基于联萘胺和H_8-联萘胺的氮杂环卡宾金属络合物的合成及应用
|
摘要
本论文主要围绕由联萘胺及H8-联萘胺衍生的氮杂环卡宾配体及其钯、铑金属络合物的合成,以及这些钯、铑金属络合物在催化反应中的应用来展开。主要由以下三部分工作组成。
一.基于联萘胺和H8-联萘胺的轴手性氮杂环卡宾钯络合物的合成及其在芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的不对称1,4-加成中的应用
从H8-联萘胺出发合成了新型轴手性氮杂环卡宾金属钯络合物Ⅰ-10和Ⅰ-11,其结构得到NMR, EA, MS, IR以及X-ray单晶衍射确认。将络合物Ⅰ-1,Ⅰ-2,Ⅰ-3,Ⅰ-4,Ⅰ-10,Ⅰ-11应用于芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的的不对称共轭加成,发现金属钯络合物Ⅰ-1,Ⅰ-10,Ⅰ-11无催化活性,而bis(NHC)-Pd(II)络合物Ⅰ-2,Ⅰ-3和Ⅰ-4可以高效催化芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的不对称共轭加成,取得了高达96%的收率,>99.5%的ee值。
二.基于联萘胺和H8-联萘胺的轴手性氮杂环卡宾铑络合物的合成及其在β-酮酯的不对称硅氢化反应中的应用
从(R)-H8-联萘胺出发,合成了轴手性的氮杂环卡宾金属铑络合物Ⅱ-2。其结构经NMR,EA, MS, IR以及X-ray单晶衍射确认。并将金属铑络合物Ⅱ-1和Ⅱ-2应用于p-酮酯的不对称硅氢化反应,发现金属铑络合物Ⅱ-1和Ⅱ-2均具有优秀的不对称催化效果,取得了良好的收率和高达99%的ee值。
三.基于联萘胺的轴手性氮杂环卡宾钯络合物在Suzuki和Heck-Mizoroki反应中的应用
将双齿氮杂环卡宾金属钯络合物Ⅰ-1应用于催化Suzuki偶联反应,芳基溴化物和芳基碘化物分别与苯基硼酸的偶联取得了高达95%的收率；而且芳基氯化物与苯基硼酸的偶联也取得了中等的收率。同时,我们把双齿氮杂环卡宾金属钯络合物Ⅰ-1应用于催化Heck-Mizoroki偶联反应,也取得了高达99%的收率。
This thesis mainly focused on the synthesis of axially chiral NHC-Rh(Ⅲ) and NHC-Pd(Ⅱ) complexes derived from BINAM and Hg-BINAM and applications of these complexes in the catalytic reactions. 1. An Efficient Asymmetric 1,4-Addition of Arylboronic Acids to 2,3-Dihydro-4-pyridones Catalyzed by Axially Chiral NHC-Pd (Ⅱ) Complexes.
Novel axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-palladium(Ⅱ) complexesⅠ-10 andⅠ-11 derived from Hg-BINAM have been synthesized. Their structures have been characterized by X-ray diffraction of single crystals. Axially chiral NHC-Pd(Ⅱ) complexesⅠ-2,Ⅰ-3 andⅠ-4 are effective catalysts for the asymmetric conjugate addition of arylboronic acids to 2,3-dihydro-4-pyridones, producing the synthetically and biologically important 2-aryl-4-piperidones in moderate to high yields (up to 96%) and with excellent enantioselectivities (up to> 99.5%ee), in most cases under mild conditions. However, bis(NHC)-Pd(Ⅱ) complexesⅠ-1,Ⅰ-10 andⅠ-11 were ineffective in this reaction. 2. Synthesis of Novel Axially Chiral NHC-Rh(Ⅲ) Complexes Derived from BINAM and Hg-BINAM and Application in the Enantioselective Hydrosilylation of 3-Oxo-3-arylpropionic Acid Methyl or Ethyl Esters.
Novel axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-Rhodium (Ⅲ) complexesⅡ-2 derived from Hg-BINAM have been synthesized. Their structures have been characterized by X-ray diffraction of single crystals. Axially chiral N-heterocyclic carbene (NHC)-Rh(Ⅲ) complexesⅡ-11 andⅡ-2 were applied in the enantioselective hydrosilylation of 3-oxo-3-arylpropionic acid methyl or ethyl esters. The reduction products, 3-hydroxy-3-arylpropionic acid methyl or ethyl esters, could be obtained in good yields (up to 90%) with good to excellent enantioselectivities (up to 99%ee) under mild conditions. 3. A Novel cis-Chelated Pd(Ⅱ)-NHC Complex for Catalyzing Suzuki and Heck-type Cross-coupling Reactions.
Axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-palladium(Ⅱ) complexⅠ-1 is fairly effective in Suzuki cross-coupling reaction. Using either aryl bromides or iodobenzene as substrates afforded coupling products in 75-99%yields, moreover, using aryl chlorides afforded moderate yields of the coupling products. ComplexⅠ-1 was also effective in Heck-type cross-coupling reaction to give the corresponding products in good to excellent yields (up to 99%) in most cases.
一.基于联萘胺和H8-联萘胺的轴手性氮杂环卡宾钯络合物的合成及其在芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的不对称1,4-加成中的应用
从H8-联萘胺出发合成了新型轴手性氮杂环卡宾金属钯络合物Ⅰ-10和Ⅰ-11,其结构得到NMR, EA, MS, IR以及X-ray单晶衍射确认。将络合物Ⅰ-1,Ⅰ-2,Ⅰ-3,Ⅰ-4,Ⅰ-10,Ⅰ-11应用于芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的的不对称共轭加成,发现金属钯络合物Ⅰ-1,Ⅰ-10,Ⅰ-11无催化活性,而bis(NHC)-Pd(II)络合物Ⅰ-2,Ⅰ-3和Ⅰ-4可以高效催化芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的不对称共轭加成,取得了高达96%的收率,>99.5%的ee值。
二.基于联萘胺和H8-联萘胺的轴手性氮杂环卡宾铑络合物的合成及其在β-酮酯的不对称硅氢化反应中的应用
从(R)-H8-联萘胺出发,合成了轴手性的氮杂环卡宾金属铑络合物Ⅱ-2。其结构经NMR,EA, MS, IR以及X-ray单晶衍射确认。并将金属铑络合物Ⅱ-1和Ⅱ-2应用于p-酮酯的不对称硅氢化反应,发现金属铑络合物Ⅱ-1和Ⅱ-2均具有优秀的不对称催化效果,取得了良好的收率和高达99%的ee值。
三.基于联萘胺的轴手性氮杂环卡宾钯络合物在Suzuki和Heck-Mizoroki反应中的应用
将双齿氮杂环卡宾金属钯络合物Ⅰ-1应用于催化Suzuki偶联反应,芳基溴化物和芳基碘化物分别与苯基硼酸的偶联取得了高达95%的收率；而且芳基氯化物与苯基硼酸的偶联也取得了中等的收率。同时,我们把双齿氮杂环卡宾金属钯络合物Ⅰ-1应用于催化Heck-Mizoroki偶联反应,也取得了高达99%的收率。
This thesis mainly focused on the synthesis of axially chiral NHC-Rh(Ⅲ) and NHC-Pd(Ⅱ) complexes derived from BINAM and Hg-BINAM and applications of these complexes in the catalytic reactions. 1. An Efficient Asymmetric 1,4-Addition of Arylboronic Acids to 2,3-Dihydro-4-pyridones Catalyzed by Axially Chiral NHC-Pd (Ⅱ) Complexes.
Novel axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-palladium(Ⅱ) complexesⅠ-10 andⅠ-11 derived from Hg-BINAM have been synthesized. Their structures have been characterized by X-ray diffraction of single crystals. Axially chiral NHC-Pd(Ⅱ) complexesⅠ-2,Ⅰ-3 andⅠ-4 are effective catalysts for the asymmetric conjugate addition of arylboronic acids to 2,3-dihydro-4-pyridones, producing the synthetically and biologically important 2-aryl-4-piperidones in moderate to high yields (up to 96%) and with excellent enantioselectivities (up to> 99.5%ee), in most cases under mild conditions. However, bis(NHC)-Pd(Ⅱ) complexesⅠ-1,Ⅰ-10 andⅠ-11 were ineffective in this reaction. 2. Synthesis of Novel Axially Chiral NHC-Rh(Ⅲ) Complexes Derived from BINAM and Hg-BINAM and Application in the Enantioselective Hydrosilylation of 3-Oxo-3-arylpropionic Acid Methyl or Ethyl Esters.
Novel axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-Rhodium (Ⅲ) complexesⅡ-2 derived from Hg-BINAM have been synthesized. Their structures have been characterized by X-ray diffraction of single crystals. Axially chiral N-heterocyclic carbene (NHC)-Rh(Ⅲ) complexesⅡ-11 andⅡ-2 were applied in the enantioselective hydrosilylation of 3-oxo-3-arylpropionic acid methyl or ethyl esters. The reduction products, 3-hydroxy-3-arylpropionic acid methyl or ethyl esters, could be obtained in good yields (up to 90%) with good to excellent enantioselectivities (up to 99%ee) under mild conditions. 3. A Novel cis-Chelated Pd(Ⅱ)-NHC Complex for Catalyzing Suzuki and Heck-type Cross-coupling Reactions.
Axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-palladium(Ⅱ) complexⅠ-1 is fairly effective in Suzuki cross-coupling reaction. Using either aryl bromides or iodobenzene as substrates afforded coupling products in 75-99%yields, moreover, using aryl chlorides afforded moderate yields of the coupling products. ComplexⅠ-1 was also effective in Heck-type cross-coupling reaction to give the corresponding products in good to excellent yields (up to 99%) in most cases.
引文
[1]Ofele, K. 1,3-Dimethyl-4-imidazolin-yliden-(2)-pentacarbonyl Chromein, Neuer Ubergangsmetall-carbene-complex. J. Organomet. Chem.1968,12,42-43.
[2]Wanzlick, H. W.; Schnherr, H. J. Chemistry of Nucleophilic Carbene XIV. Direct Synthesis of a Mercury Salt-Carbene Complex. Angew. Chem. Int. Ed. Engl.1968,7, 141-142.
[3](a) Arduengo, A. J. Ⅲ.; Harlow, R. L.; Kline, M. A Stable Crystsline Carbene. J. Am. Chem. Soc.1991,113,361-363. (b) Arduengo, A. J. Ⅲ.; Kline, M.; Calabress, J. C. Synthesis of a Reverse Ylide from a Nucleophilic Carbene. J. Am. Chem. Soc.1991,113, 9704-9705. (c) Arduengo, A. J. Ⅲ.; Krafczyk, R.; Schmutzler, R. Imidazolylidenes, Imidazolinylidenes and Imidazolidines. Tetrahedron 1999,55,14523-14534.
[4]Herrmann, W. A.; Elison, M.; Fischer, J.; Kocher, C.; Artus, G. R. Metal Complexes of N-Heterocyclic Carbenes-A New Structural Principle for Catalysts in Homogeneous Catalysis J. Angew. Chem., Int. Ed. Engl.1995,34, 2371-2374.
[5]Teles, J. H.; Melder, J.-P.; Ebel, K.; Schneider, R.; Gehrer, E.; Harder, W.; Brode, S.; Enders, D.; Breuer, K.; Raabe, G. New Mechanistic Proposal for Some Heptamolybdate-Ion-Catalyzed Isomerizations. Helv. Chim. Acta.1996,79,61-83.
[6]Kiiciikbay, H.; C, etinkaya, B.; Guesmi, S.; Dixneuf, P. H. New (Carbene) RutheniumArene Complexes:Preparation and Uses in Catalytic Synthesis of Furans. Organometallics 1996,15,2434-2439.
[7](a) Herrmann, W. A. N-Heterocyclic Carbenes:A New Concept in Organometallic Catalysis. Angew. Chem., Int. Ed.2002,41,1290-1309. (b) Herrmann, W. A.; Kocher, C. N-Heterocyclic Carbenes. Angew. Chem., Int. Ed. Engl.1997,36,2162-2187.
[8]Crabtree, R. H. NHC Ligands Versus Cyclopentadienyls and Phosphines as Spectator Ligands in Organometallic Catalysis. J. Organomet. Chem.2005,690,5451-5457.
[9](a) Herrmann, W. A. N-Heterocyclic Carbenes:A new Concept in Organometallic Catalysts. Angew. Chem. Int. Ed.2002,40,1290-1309. (b) Despagnet-Ayoub, E.; Grubbs, R. H. A Stable Four-Membered N-Heterocyclic Carbene. J. Am. Chem. Soc.2004,126, 10198-10199. (c) Despagnet-Ayoub, E.; Grubbs, R. H. A Ruthenium Olefin Metathesis Catalyst with a Four-membered N-heterocyclic Carbene Ligand. Organometallics 2005, 24,338-340. (d) Alder, R. W.; Blake, M. E.; Bortolotti, C.; Bufali, S.; Butts, C. P.; Linehan, E.; Oliva, J. M.; Orpen, A. G; Quayle, M. J. Complexation of Stable Carbenes with Alkali Metals. Chem. Commun.1999,241-242. (e) Bazinet, P.; Yap, G P. A.; Richeson, D. S. Constructing a Stable Carbene with a Novel Topology and Electronic Framework. J. Am. Chem. Soc.2003,125,13314-13315.
[10](a) Enders, D.; Niemeier,O.; Henseler, A. Organocatalysis by N-Heterocyclic Carbenes. Chem. Rev.2007,107,5606. (b) Marion, N.; Diez-Gonzalez, S.; Nolan, S. P. N-Heterocyclic Carbenes as Organocatalysts. Angew. Chem. Int. Ed.2007,46,2988. (c) Hahn, F. E.; Jahnke, M. C. Heterocyclic Carbenes:Synthesis and Coordination Chemistry. Angew. Chem. Int. Ed.2008,47,3122. (d) Liddle, S. T.; Edworthy, I. S.; Arnold, P. L. Anionic Tethered N-heterocyclic Carbene Chemistry. Chem. Soc. Rev. 2007,36,1732.
[11]Breslow, R. On the Mechanism of Thiamine Action IV Evidence from Studies on Model Systems. J. Am. Chem. Soc.1958,80,3719.
[12]Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H. The First Asymmetric Intramolecular Stetter Reaction Preliminary Communication. Helv. Chim. Acta.1996,79,1899-1902.
[13]Enders, D.; Kallfass, U. An Efficient Nucleophilic Carbene Catalyst for the Asymmetric Benzoin Condensation. Angew. Chem. Int. Ed.2002,41,1743-1745.
[14]Burstein, C.; Glorius, R. Organocatalyzed Conjugate Umpolung of unsaturated Aldehydes for the Synthesis of y-butyrolactones. Angew. Chem. Int. Ed.2004,43, 6205-6208.
[15]Suzuki, Y.; Toyota, T.; Imada, F.; Sato, M.; Miyashita, A. Nucleophilic Acylation of Arylfluorides Catalyzed by Imidazolidenyl Carbene. Chem. Commun.2003,1314-1315.
[16]Connor, E. F.; Nyce, G. W.; Myers, M.; Mock, A; Hedrick, J. L. First Example of N-Heterocyclic Carbenes as Catalysts for Living Polymerization:Organocatalytic Ring-Opening Polymerization of Cyclic Esters. J. Am. Chem. Soc.2002,124,914.
[17](a)Herrmannn, W. A.; Elison, M.; Fischer, J.; Kocher, C.; Artus, G. R. J. Metal Complexes of N-heterocyclic Carbenes:A New Structural Principle for Catalysts in Homogeneous Catalysis. Angew. Chem. Int. Ed. Engl.1995,34,2371-2374. (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.; Trudell, M. L.; Nolan, S. P. Suzuki-Miyaura Cross-Coupling Reactions Mediated by Palladium/Imidazolium Salt Systems Organometallics 2002,21,2866-2873. (c) Vargas, V. C.; Rubio, R. J.; Hollis, T. K.; Salcido, M. E. Efficient Route to 1,3-Di-N-imidazolylbenzene. A Comparison of Monodentate vs Bidentate Carbenes in Pd-Catalyzed Cross Coupling Org. Lett.2003,5, 4847-4849. (d) Navarro, O.; Kelly, R. A.; Nolan, S. P. A General Method for the Suzuki-Miyaura Cross-Coupling of Sterically Hindered Aryl Chlorides:Synthesis of Di-and Tri-ortho-substituted Biaryls in 2-Propanol at Room Temperature J. Am. Chem. Soc.2003,125,16194-16195. (e) Marion, N.; Nolan, S. P. Acc. Chem. Res.2008,41, 1440-1449; (f) Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G. Palladium Complexes of N-Heterocyclic Carbenes as Catalysts for Cross-Coupling Reactions A Synthetic Chemist's Perspective Angew. Chem., Int. Ed.2007,46,2768-2813. (g) Navarro, O.; Kelly, R. A.; Nolan, S. P. A General Method for the Suzuki-Miyaura Cross-Coupling of Sterically Hindered Aryl Chlorides:Synthesis of Di-and Tri-ortho-substituted Biaryls in 2-Propanol at Room Temperature J. Am. Chem. Soc.2003,125,16194-16195 (h) Altenhoff, G.; Goddard, R.; Lehmann, C. W.; Glorius, F. Sterically Demanding, Bioxazoline-Derived N-Heterocyclic Carbene Ligands with Restricted Flexibility for Catalysis J. Am. Chem. Soc.2004,126,15195-15201. (i) Marion, N.; Navarro, O.; Mei, J.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. Modified (NHC)Pd(allyl)Cl (NHC= N-Heterocyclic Carbene) Complexes for Room-Temperature Suzuki-Miyaura and Buchwald-Hartwig Reactions J. Am. Chem. Soc.2006,128,4101-4111. (j) Percec, V.; Golding, G. M.; Smidrkal, J.; Weichold, O. NiCl2(dppe)-Catalyzed Cross-Coupling of Aryl Mesylates, Arenesulfonates, and Halides with Arylboronic Acids J. Org. Chem. 2004,69,3447-3452. (k) Blakey, S. B.; MacMillan, D. W. C. The First Suzuki Cross-Couplings of Aryltrimethylammonium Salts J. Am. Chem. Soc.2003,125, 6046-6047. (1) Liu, J.; Robins, M. J. zoles as Suzuki Cross-Coupling Leaving Groups: Syntheses of 6-Arylpurine 2'-Deoxynucleosides and Nucleosides from 6-(Imidazol-1-yl)-and 6-(1,2,4-Triazol-4-yl)purine Derivativesl Org. Lett.2004,6, 3421-3423. (m) N-Heterocyclic Carbenes in Synthesis; Nolan, S. P., Ed.; Wiley-VCH: Weinheim,2006. (n) Herrmann, W. A. N-Heterocyclic Carbenes:A New Concept in Organometallic Catalysis Angew. Chem., Int. Ed.2002,41,1290. (m) Bohm, V. P. W.; Weskamp, T.; Gsto"ttmayr, C. W. K.; Herrmann, W. A. Nickel-Catalyzed Cross-Coupling of Aryl Chlorides with Aryl Grignard Reagents Angew. Chem., Int. Ed. 2000,39,1602-1604. (o) Bohm, V. P.W.; Gstottmayr, C. W. K.; Weskamp, T.; Herrmann, W. A. Catalytic C-C Bond Formation through Selective Activation of C-F Bonds Angew. Chem., Int. Ed.2001,40,3387-3389. (p) Kiyofumi, I.; Jun-ichi, K.; Takao, S.; Kou, K. Catalytic Activities of a Bis(carbene)-Derived Nickel(II)-Pincer Complex in Kumada-Tamao-Corriu and Suzuki-Miyaura Coupling Reactions for the Synthesis of Biaryl Compounds Synthesis 2007,2853-2861. (q) Matsubara, K.; Ueno, K.; Shibata, Y. Synthesis and Structures of Nickel Halide Complexes Bearing Mono-and Bis-coordinated N-Heterocyclic Carbene Ligands, Catalyzing Grignard Cross-Coupling Reactions Organometallics 2006,25,3422-3427. (r) Rudolph, A.; Lautens, M. Secondary Alkyl Halides in Transition-Metal-Catalyzed Cross-Coupling Reactions Angew. Chem., Int. Ed.2009,48,2656-2670. (s) Glorius, F. Asymmetric Cross-Coupling of Non-Activated Secondary Alkyl Halides Angew. Chem., Int. Ed. 2008,47,8347-8349. (t) Frisch, A. C.; Beller, M. Catalysts for Cross-Coupling Reactions with Non-activated Alkyl Halides Angew. Chem., Int. Ed.2005,44,674-688. (u) Bedford, R. B.; Betham, M.; Bruce, D. W.; Danopoulos, A. A.; Frost, R. M.; Hird, M. Iron-Phosphine,-Phosphite,-Arsine, and-Carbene Catalysts for the Coupling of Primary and Secondary Alkyl Halides with Aryl Grignard Reagents J. Org. Chem.2006, 71,1104-1110. (v) Hatakeyama, T.; Nakamura, M. Iron-Catalyzed Selective Biaryl Coupling:Remarkable Suppression of Homocoupling by the Fluoride Anion J. Am. Chem. Soc.2007,129,9844-9845. (w) Yamagami, T.; Shintani, R.; Shirakawa, E.; Hayashi, T. Iron-Catalyzed Arylmagnesiation of Aryl(alkyl)acetylenes in the Presence of an N-Heterocyclic Carbene Ligand Org. Lett.2007,9,1045-1048.
[18](a) Herrmann, W. A.; Goossen, L. T.; Kocher, C.; Artus, G. R. J. Chiral heterocyclic carbenes in asymmetric homogeneous catalysis. Angew. Chem. Int. Ed. Engl.1996,35, 2805-2807. (b) Gade, L. H.; Cesar, V.; Bellemin-Laponnaz, S. A Modular Assembly of Chiral Oxazolinylcarbene-Rhodium Complexes:Efficient Phosphane-Free Catalysts for the Asymmetric Hydrosilylation of Dialkyl Ketones Angew. Chem., Int. Ed.2004,43, 1014-1017. (c) Enders, D.; Gielen, H. Synthesis of Chiral Triazolinylidene and Imidazolinylidene Transition metal Complexes and First Application in Asymmetric Catalysis. J. Organomet. Chem.2001,617-618,70-80. (d) Schneider, N.; Finger, M.; Haferkemper, C.; Bellemin-Laponnaz, S.; Hofmann, P.; Gade, L. H. Metal Silylenes Generated by Double Silicon-Hydrogen Activation:Key Intermediates in the Rhodium-Catalyzed Hydrosilylation of Ketones Angew. Chem., Int. Ed.2009,48, 1609-1613. (e) Duan, W.-L.; Shi, M.; Rong, G.-B. Synthesis of Novel Axially Chiral Rh-NHC Complexes Derived from BINAM and Application in the Enantioselective Hydrosilylation of Methyl Ketones. Chem. Commun.2003,2916-2917. (f) Yuan, Y.; Raabe, G.; Bolm, C. Novel rhodium complexes with ferrocene-based N-heterocylic carbenes:Synthesis, structure and catalysis J. Organomet. Chem.2005,690,5747-5752. (g) Faller, J. W.; Fontaine, P. P. Stereodynamics and Asymmetric Hydrosilylation with Chiral Rhodium Complexes Containing a Monodentate N-Heterocyclic Carbene Organometallics 2006,25,5887-5893. (h) Nonnenmacher, M.; Kunz, D.; Rominger, F. Synthesis and Catalytic Properties of Rhodium(I) and Copper(I) Complexes Bearing Dipyrido-Annulated N-Heterocyclic Carbene Ligands Organometallics 2008,27, 1561-1568. (i) Ros, A.; Alcazaro, M.; Iglesias-Siguenza, J.; Diez, E.; Alvarez, E.; Ferna'ndez, R.; Lassaletta, J. M. Stereoselective Synthesis of Rhodium(I) 4-(Dialkylamino)triazol-5-ylidene Complexes Organometallics 2008,27,4555-4564. (j) Jime'nez, M. V.; Perez-Torrente, J. J.; Bartolome, M. I.; Gierz, V.; Lahoz, F. J.; Oro, L. A. Rhodium(I) Complexes with Hemilabile N-Heterocyclic Carbenes:Efficient Alkyne Hydrosilylation Catalysts Organometallics 2008,27,224-234. (k) Hu, J. J.; Li, F.; Hor, T. S. A. Novel Pt(II) Mono-and Biscarbene Complexes:Synthesis, Structural Characterization and Application in Hydrosilylation Catalysis Organometallics 2009,28, 1212-1220. (1) Poyatos, M.; Maisse-Franc.ois, A.; Bellemin-Laponnaz, S.; Gade, L. H. Coordination Chemistry of a Modular N,C-Chelating Oxazole-Carbene Ligand and Its Applications in Hydrosilylation Catalysis Organometallics 2006,25,2634-2641. (m) De Bo, G.; Berthon-Gelloz, G.; Tinant, B.; Marko, I. E. Hydrosilylation of Alkynes Mediated by N-Heterocyclic Carbene Platinum(0) Complexes Organometallics 2006,25, 1881-1890. (n) Berthon-Gelloz, G.; Schumers, J.-M.; De Bo, G.; Marko, I. E. Highly β-(E)-Selective Hydrosilylation of Terminal and Internal Alkynes Catalyzed by a (IPr)Pt(diene) Complex J.Org. Chem.2008,73,4190-4197.
[19](a) Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Synthesis of Cyclic Polybutadiene via Ring-Opening Metathesis Polymerization:The Importance of Removing Trace Linear Contaminants J. Am. Chem. Soc.2003,125,8424-8425. (b) Boydston, A. J.; Xia, Y.; Kornfield, J. A.; Gorodetskaya, I. A.; Grubbs, R. H. Cyclic Ruthenium-Alkylidene Catalysts for Ring-Expansion Metathesis Polymerization J. Am. Chem. Soc.2008,130,
12775-12782. (c) Occhipinti, G.; Bj(?)rsvik, H. R.; Tomroos, K. W.; Furstner, A. Jensen, V. R. The First Imidazolium-Substituted Metal Alkylidene Organometallics 2007,26,4383-4385. (d) Yun, S. Y.; Kim, M.; Lee, D.; Wink, D. J. Structure and Reactivity of Alkynyl Ruthenium Alkylidenes J. Am. Chem. Soc.2009,131,24-25. (e) Bolton, S. L.; Williams, J. E.; Sponsler, M. B. Stabilization of (Trialkylphosphine)ruthenium Alkylidene Metathesis Catalysts using Phosphine Exchange Organometallics 2007,26,2485-2487. (f) Rix, D.; Caijo, F.; Laurent, I.; Boeda, F.; Clavier, H.; Nolan, S. P.; Mauduit, M. Aminocarbonyl Group Containing Hoveyda-Grubbs-Type Complexes:Synthesis and Activity in Olefin Metathesis Transformations J.Org. Chem.2008,73,4225-4228.
[20](a) Tsarevsky, N. V.; Matyjaszewski, K. "Green" Atom Transfer Radical Polymerization:From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials Chem. Rev.2007,107,2270-2299. (b) McGuinness, D. S.; Gibson, V. C.; Steed, J. W. Bis(carbene)pyridine Complexes of the Early to Middle Transition Metals:Survey of Ethylene Oligomerization and Polymerization Capability Organometallics 2004,23,6288-6292. (c) Danopoulos, A. A.; Tsoureas, N.; Wright, J. A.; Light, M. E. N-Heterocyclic Pincer Dicarbene Complexes of Iron(II):C-2 and C-5 Metalated Carbenes on the Same Metal Center Organometallics 2004,23,166-168. (d) Chen, M.-Z.; Sun, H.-M.; Li, W.-F.; Wang, Z.-G.; Shen, Q.; Zhang, Y. Synthesis, structure of functionalized N-heterocyclic carbene complexes of Fe(II) and their catalytic activity for ring-opening polymerization of ε-caprolactone J. Organomet. Chem.2006, 691,2489-2494. (e) Csabai, P.; Joo, F.; Trzeciak, A. M.; Ziolkowski, J. J. Catalytic activity of a half-sandwich Ru(Ⅱ)-N-heterocyclic carbene complex in the oligomerization of alkynes J. Organomet. Chem.2006,691,3371-3376. (f) Zhang, Y.; Wang, D.; Wurst, K.; Buchmeiser, M. R. Polymerization of phenylacetylene by novel Rh (I)-, Ir (I)-and Ru (Ⅳ) 1,3-R2-3,4,5,6-tetrahydropyrimidin-2-ylidenes(R= mesityl, 2-propyl):Influence of structure on activity and polymer structure J. Organomet. Chem. 2005,690,5728-5735. (g) Becker, E.; Stingl, V.; Dazinger, G.; Puchberger, M.; Mereiter, K.; Kirchner, K. Facile Migratory Insertion of a N-Heterocyclic Carbene into a Ruthenium-Carbon Double Bond:A New Type of Reaction of a NHC Ligand J. Am. Chem. Soc.2006,128,6572-6573. (h) Becker, E.; Stingl, V.; Mereiter, K.; Kirchner, K. Formation of a Half-Sandwich Triscarbene Ruthenium Complex:Oxidative Coupling of 2,7-Nonadiyne Mediated by [RuCp(IPri)(CH3CN)2]+(IPri= 1,3-bis(2,6-diisopropylphenyl) imidazol-2-ylidene) Organometallics 2006,25, 4166-4169.
[21](a) Poyatos, M.; Maisse-Francois, A.; Bellemin-Laponnaz, S.; Peris, E.; Gade, L. H.Synthesis and structural chemistry of arene-ruthenium half-sandwich complexes bearing an oxazolinyl-carbene ligand J. Organomet. Chem.2006,691,2713-2720. (b) Cheng, Y.; Sun, J.-F.; Yang, H.-L.; Xu, H.-J.; Li, Y.-Z.; Chen, X.-T.; Xue, Z.-L Syntheses, Structures, and Catalytic Properties of Ruthenium(II) Nitrosyl Complexes with Pyridine-Functionalized N-Heterocyclic Carbenes Organometallics 2009,28, 819-823. (c) Enthaler, S.; Jackstell, R.; Hagemann, B.; Junge, K.; Erre, G.; Beller, M. Efficient transfer hydrogenation of ketones in the presence of ruthenium N-heterocyclic carbene catalysts J. Organomet. Chem.2006,691,4652-659. (d) Zeng, F.; Yu, Z. Ruthenium(II) Complexes Bearing a Pyridyl-Supported Pyrazolyl-N-Heterocyclic Carbene (NNC) Ligand and Their Catalytic Activity in the Transfer Hydrogenation of Ketones Organometallics 2008,27,6025-6028. (e) Lee, H. M.; Smith, D. C., Jr.; Ho, Z.; Stevens, E. D.; Yi, C. S.; Nolan, S. P. Catalytic Hydrogenation of Alkenes by the Ruthenium-Carbene Complex HRu(CO)Cl(PCy3)(IMes) (IMes= Bis(1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene) Organometallics 2001,20,794-797. (f) Banti, D.; Mol, J. C. Degradation of the ruthenium-based metathesis catalyst [RuCl2(=CHPh)(H2IPr)(PCy3)] with primary alcohols J. Organomet. Chem.2004,689, 3113-3116. (g) Dharmasena, U. L.; Foucault, H.; dos Santos, E. N.; Fogg, D. E.; Nolan, S. P. N-Heterocyclic Carbenes as Activating Ligands for Hydrogenation and Isomerization of Unactivated Olefins Organometallics 2005,24,1056-1058. (h) Burling, S.; Paine, B. M.; Nama, D.; Brown, V. S.; Mahon, M. F.; Prior, T. J.; Pregosin, P. S.; Whittlesey, M. K.; Williams, J. M. J. C-H Activation Reactions of Ruthenium N-Heterocyclic Carbene Complexes:Application in a Catalytic Tandem Reaction Involving C-C Bond Formation from Alcohols J. Am. Chem. Soc.2007,129, 1987-1995. (i) Jazzar, R. F. R.; Macgregor, S. A.; Mahon, M. F.; Richards, S. P.; Whittlesey, M. K. C-C and C-H Bond Activation Reactions in N-Heterocyclic Carbene Complexes of Ruthenium J. Am. Chem. Soc.2002,124,4944-4945. (j) Viciano, M.; Sanau', M.; Peris, E. Ruthenium Janus-Head Complexes with a Triazolediylidene Ligand. Structural Features and Catalytic Applications Organometallics 2007,26,6050-6054. (k) Prades, A.; Viciano, M.; Sanau, M.; Peris, E. Preparation of a Series of "Ru(p-cymene)" Complexes with Different N-Heterocyclic Carbene Ligands for the Catalytic β-Alkylation of Secondary Alcohols and Dimerization of Phenylacetylene Organometallics 2008,27,4254-4259. (1) Gnanamgari, D.; Sauer, E. L. O.; Schley, N. D.; Butler, C.; Incarvito, C. D.; Crabtree, R. H. Iridium and Ruthenium Complexes with Chelating N-Heterocyclic Carbenes: Efficient Catalysts for Transfer Hydrogenation,β-Alkylation of Alcohols, and N-Alkylation of Amines Organometallics 2009,28,321-325. (m) Bappert, E.; Helmchen, G. Synthesis and Application of Complexes of a Novel Chiral Diphenylphosphino-Functionalized N-Heterocyclic Carbene Synlett 2004,1789-1793. (n) Poyatos, M.; Mc-Namara, W.; Incarvito, C.; Clot, E.; Peris, E.; Crabtree, R. H. A Weak Donor, Planar Chelating Bitriazole N-Heterocyclic Carbene Ligand for Ruthenium(II), Palladium(II), and Rhodium Organometallics 2008,27,2128-2136.
[22](a) Meyer, D.; Taige, M. A.; Zeller, A.; Hohlfeld, K.; Ahrens, S.; Strassner, T. Palladium Complexes with Pyrimidine-Functionalized N-Heterocyclic Carbene Ligands:Synthesis, Structure and Catalytic Activity Organometallics 2009,28,2142-2149. (b) Campeau, L.-C.; Thansandote, P.; Fagnou, K. High-Yielding Intramolecular Direct Arylation Reactions with Aryl Chlorides Org. Lett.2005,7,1857-1860.
[23](a) Dastgir, S.; Coleman, K. S.; Cowley, A. R.; Green, M. L. H. A Stable Crystalline Imino-N-Heterocyclic Carbene Ligand and Its Corresponding Palladium(II) and Rhodium(I) ComplexesOrganometallics 2006,25,300-306. (b) Green, M.; McMullin, C. L.; Morton, G. J. P.; Orpen, A. G.; Wass, D. F.; Wingad, R. L Rhodium Complexes of Cyclopropenylidene Carbene Ligands:Synthesis, Structure, and Hydroformylation Catalysis Organometallics 2009,28,1476-1479. (c) Sparta, M.; B(?)rve, K. J.; Jensen, V. R. Activity of Rhodium-Catalyzed Hydroformylation:Added Insight and Predictions from Theory J. Am. Chem. Soc.2007,129,8487-8499.
[24](a) Tudose, A.; Demonceau, A.; Delaude, L. Imidazol(in)ium-2 -carboxylates as N-heterocyclic carbene precursors in ruthenium-arene catalysts for olefin metathesis and cyclopropanation J. Organomet. Chem.2006,691,5356.
[25](a) Sato, Y.; Yoshino, T.; Mori, M. Pd-Catalyzed Allylic Substitution Using Nucleophilic N-Heterocyclic Carbene as a Ligand Org. Lett.2003,5,31-33. (b) Sato, Y.; Yoshino, T.; Mori, M. N-Heterocyclic carbenes as ligands in palladium-catalyzed Tsuji-Trost allylic substitution J. Organomet. Chem.2005,690,5753-5758. For the related allylic amination, see:(c) Visentin, F.; Togni, A. Synthesis and Characterization of Palladium(II) π-Allyl Complexes with Chiral Phosphinocarbene Ligands. Kinetics and Mechanism of Allylic Amination Organometallics 2007,26,3746-3754. (358) Flahaut, A.; Roland, S.; Mangeney, P. Allylic alkylation and amination using mixed (NHC)(phosphine) palladium complexes under biphasic conditions J. Organomet. Chem.2007,692, 5754-5762. (359) Roland, S.; Cotet, W.; Mangeney, P. Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N-Heterocyclic Carbene Ligands Eur. J. Inorg. Chem.2009,1796-1805. (360) Toselli, N.; Martin, D.; Buono, G. Looking for a Synergic Effect between NHCs and Chiral P-Ligands Org. Lett.2008,10,1453-1456.
[26](a) Hanasaka, F.; Fujita, K.-i.; Yamaguchi, R. Cp*Ir Complexes Bearing N-Heterocyclic Carbene Ligands as Effective Catalysts for Oppenauer-Type Oxidation of Alcohols Organometallics 2004,23,1490-1492. (b) Hanasaka, F.; Fujita, K.-i.; Yamaguchi, R. Synthesis of New Cationic Cp*Ir N-Heterocyclic Carbene Complexes and Their High Catalytic Activities in the Oppenauer-Type Oxidation of Primary and Secondary Alcohols Organometallics 2005,24,3422-3433. (c) Hanasaka, F.; Fujita, K.-i.; Yamaguchi, R. Synthesis of New Iridium N-Heterocyclic Carbene Complexes Bearing a Functionalized Cp* Ligand and Their High Catalytic Activities in the Oppenauer-Type Oxidation of Alcohol Organometallics 2006,25,4643-4647. (d) Iwai, Y.; Gligorich, K. M.; Sigman, M. S. Aerobic Alcohol Oxidation Coupled to Palladium-Catalyzed Alkene Hydroarylation with Boronic Esters Angew. Chem., Int. Ed.2008,47,3219-3222. (e) Popp, B. V.; Stahl, S. S. Insertion of Molecular Oxygen into a Palladium-Hydride Bond:Computational Evidence for Two Nearly Isoenergetic Pathways J. Am. Chem. Soc.2007,129,4410-4422. (f) Konnick, M. M.; Stahl, S. S. Reaction of Molecular Oxygen with a PdⅡ-Hydride To Produce a PdⅡ-Hydroperoxide: Experimental Evidence for an HX-Reductive-Elimination Pathway J. Am. Chem. Soc. 2008,130,5753-5762. (g) Popp, B. V.; Wendlandt, J. E.; Landis, C. R.; Stahl, S. S. Reaction of Molecular Oxygen with an NHC-Coordinated Pd0 Complex: Computational Insights and Experimental Implications Angew. Chem., Int. Ed.2007,46, 601-604. (h) Konnick, M. M.; Gandhi, B. A.; Guzei, I. A.; Stahl, S. S. Reaction of Molecular Oxygen with a PdⅡ-Hydride To Produce a PdⅡ-Hydroperoxide:Acid Catalysis and Implications for Pd-Catalyzed Aerobic Oxidation Reactions Angew. Chem., Int. Ed.2006,45,2904-2907.
[27](a) Fournier, P.-A.; Collins, S. K. A Highly Active Chiral Ruthenium-Based Catalyst for Enantioselective Olefin Metathesis. Organometallics 2007,26,2945-2949. (b) Fournier, P.-A.; Savoie, J.; Stenne, B.; Bedard, M.; Grandbois, A.; Collins, S. K. Mechanistically Inspired Catalysts for Enantioselective Desymmetrizations by Olefin Metathesis. Chem. Eur. J.2008,14,8690-8695.
[28](a) Powell, M. T.; Hou, D. R.; Perry, M. C; Cui, X.; Burgess, K. Chiral Imidazolylidine Ligands for Asymmetric Hydrogenation of Aryl Alkenes. J. Am. Chem. Soc.2001,123, 8878-8879. (b) Perry, M. C; Cui, X. H.; Powell, M. T.; Hou, D. R.; Reibenspies, J. H.; Burgess, K. Optically Active Iridium Imidazol-2-ylidene-oxazoline Complexes: Preparation and Use in Asymmetric Hydrogenation of Arylalkenes. J. Am. Chem. Soc. 2003,125,113-123.
[29]Seo, H.; Kim, B. Y.; Lee, J. H.; Park, H.-J.; Son, S. U.; Chung, Y. K. Synthesis of Chiral Ferrocenyl Imidazolium Salts and Their Rhodium(Ⅰ) and Iridium(Ⅰ) Complexes. Organometallics 2003,22,4783-4791.
[30]Lee, S.; Hartwig, J. F. Improved Catalysts for the Palladium-catalyzed Synthesis of Oxindoles by Amide Arylation, Rate Acceleration, Use of Aryl Chloride Substrates and a New Carbene Ligand for Asymmetric Transformations. J. Org. Chem.2001,66, 3402-3415.
[31]Glorius, F.; Altenhoff, G.; Goddard, R.; Lethmann, C. Oxazolines as Chiral Building Blockes for Imidazolium Salts and N-heterocyclic Carbene Ligands. Chem. Commun. 2002,22,2704-2705.
[32]Larsen, A. O.; Leu, W.; Oberhuber, C. N.; Campbell, J. E.; Hoveyda, A. H. Bidentate NHC-Based Chiral Ligands for Efficient Cu-Catalyzed Enantioselective Allylic Alkylations:Structure and Activity of an Air-Stable Chiral Cu Complex. J. Am. Chem. Soc.2004,126,11130-11131.
[33](a) Guillen, F.; Winn, C. L.; Alexakis, A. Enantioselective Copper-catalyzed Conjugated Addition Using Chiral Diaminocarbene Ligands. Tetrahedron:Asymmetry 2001,12, 2083-2086. (b) Pytkowicz, J.; Roland, S.; Manganey, P.; Enantioselective Conjugated Addition of Diethylzinc Using Catalyst:silver(Ⅰ) Diaminocarbenes and Cu(OTf)2. Tetrahedron:Asymmetry 2001,12,2087-2089. (c) Alexakis, A.; Winn, C. L.; Guillen, F.; Pytkowicz, J.; Roland, S.; Mangeney, P. Asymmetric Synthesis with N-heterocyclic Carbenes, Application to The Copper-catalyzed Conjugate Addition. Adv. Synth. Catal. 2003,345,345-348.
[34]Ma, Y.; Song, C.; Ma, C.; Sun, Z.; Chai, Q.; Andrus, M. B. Asymmetric Addition of Aryl Reagents to Enones with Rhodium Dicyclophane Imidazolium Carbene Catalysis Angew. Chem. Int. Ed.2003,42,5871-5874.
[35]Zhang, T.; Shi, M. Chiral Bidentate Bis(N-Heterocyclic Carbene)-Based Palladium Complexes Bearing Carboxylate Ligands:Highly Effective Catalysts for The Enantioselective Conjugate Addition of Arylboronic Acids to Cyclic Enones. Chem. Eur. J.2008,14,3759-3764.
[36]Focken, T.; Rudolph, J.; Bolm, C. Planar Chiral Imidazolium Salts in the Asymmetric Rhodium-Catalyzed 1,2-Addition of Arylboronic Acids to Aldehydes. Synthesis 2005, 429-436.
[37](a) Arao, T.; Kondo, K.; Aoyama, T. Development of an N-heterocyclic Carbene Ligand Based on Concept of Chiral Mimetic.Tetrahedron Lett.2006,47,1417-1420.
[38]Jensen, D. R.; Sigman, M. S. Palladium Catalysts for Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Based on Mechanistic Insight. Org. Lett.2003,5, 63-65.
[39](a) Asano, N.; Nash, R. J.; Molyneux, R. J.; Fleet, G. W. J. Sugar-mimic Glycosidase Inhibitors:Natural Occurrence, Biological Activity and Prospects for Therapeutic Application. Tetrahedron:Asymmetry 2000,11,1645-1680. (b) Watson, P. S.; Jiang, B.; Scott, B. A Diastereoselective Synthesis of 2,4-Disubstituted Piperidines:Scaffolds for Drug Discovery. Org. Lett.2000,2,3679-3681.
[40](a) Mayers, A. I.; Shawe, T. T.; Gottlieb, L. Stereoselective Nucleophilic Addition to Conformationally Constrained Piperidines An Efficient Route to 2-axial-6-equatorial Disubstituted Piperidines. Tetrahedron Lett.1992,33,867. (b) Tawara, J. N.; Lorenz, P.; Stermitz, F. R. J. Piperidine Alkaloids of Spruce (Picea) and Fir (Abies) species. Nat. Prod.1999,62,321-323. (c) Watson, P. S.; Jiang, B.; Scott, B. A Diastereoselective Synthesis of 2,4-Disubstituted Piperidines:Scaffolds for Drug Discovery. Org. Lett. 2000,2,3679-3681. (d) Brooks, C. A.; Comins, D. L. Asymmetric Synthesis of (2S,4R)-4-hydroxypipecolic Acid.Tetrahedron Lett.2000,41,3551-3553. (e) Weintraub, P. M.; Sabol, J. S.; Kane, J. M.; Borcherding, D. R. Recent Advances in The Synthesis of Piperidones and Piperidines. Tetrahedron 2003,59,2953. (f) Buffat, M. G. P. Synthesis of Piperidines.Tetrahedron 2004,60,1701-1709.
[41]See, for example:(a) Pistia-Brueggeman, G.; Hollingsworth, R. I. A Preparation and Scree-ning Strategy for Glycosidase Inhibitors.Tetrahedron 2001,57,8773-8778. (b) Mukhtar, T. A.; Wright, G. D. Streptogramins, Oxazolidinones, and Other Inhibitors of Bacterial Protein Synthesis.Chem. Rev.2005,105,529-542. (c) Aridoss, G.; Balasubtamanian, S.; Parthiban, D.; Kabilan, S.Synthesis and in Vitro Microbiological Evaluation of Imidazo (4,5-b) Pyridinyleth Oxypiperidones. Eur. J. Med. Chem.2006, 41,268-275. (d) Pei, Z.; Li, X.; von Geldern, T. W.; Longenecker, K.; Pireh, D.; Stewart, K. D.; Backes, B. J.; Lai, C.; Libben, T. H.; Ballaron, S. J.; Beno, D. W. A.; Kempf-Grote, A. J.; Sham, H. L. Trevillyan, J. M. Discovery and Structure-Activity Relationships of Piperidinone-and Piperidine-Cons-trained Phenethylamines as Novel, Potent, and Selective Dipeptidyl Peptidase IV Inhibitors. Med. Chem.2007,50, 1983-1987. (e) Jha, A.; Mukherjee, C.; Prasad, A. K.; Parmar, V. S.; De Clercq, E.; Balzarini, J.; Stables, J. P.; Manavathu, E. K.; Shrivastav, A.; Sharma, R. K.; Nienaber, K. H.; Zello, G. A.; Dimmock, J. R. E,E,E-1-(4-Arylamino-4-oxo-2-butenoyl)-3,5-bis--(arylidene)-4-piperidones:A Topographical Study of Some Novel Potent Cytotoxins Bioorg. Med Chem.2007,15,5854-5865. (f) Das, U.; Das, S.; Bandy, B.; Stables, J. P.; Dimmock, J. R. N-Aroyl-3,5-bis(benzylidene)-4-piperidones:A Novel Class of Antimycobacterial Agents. Bioorg. Med. Chem.2008,16,3602-3607.
[42]Champseix, A. A.; Lefur, G. R. Eur. Pat.12,643 Synthesis and Carbon-β NMR of New C-substituted 1,3-dicyanopropanes. Chem. Abstr.1981,94,15175.
[43]Samczuk, S.; Hermans, H. K. F. Ger. Pat.2,642,856; N-Aryl-N(4-piperidinyl) Arylacetam-ides. Chem. Abstr.1977,87,53094.
[44]Ciba-Geigy, Fr. Pat.2,437,405; Basic Substituted Alkylbenzenzenes an Pharma Ceutical Compositions Containing Them. Chem. Abstr.1981,94,83739.
[45]Nalanishi, M.; Shiraki, M.; Kobayakawa, T.; Kobayashi, R. Jpn. Pat.74-03987; Improvement of Baking Processes and Preservation of Bread by Using 1,6-glucosidase.Chem. Abstr.1974,81,12085.
[46]Dimmock, J. R.; Kandepu, N. M.; Nazarali, A. J. Conformational and Quantitative Structureactivity Relationship Study of Cytotoxic 2-arylidenebenzocycloalkanones.1999, 8.
[47]Wang, Z. X. Stereoisomers of N-[1-(2-Hydroxy-2-phenylethyl)-3-methyl-4-piperidyl] N-phenylpropanamide:Synthesis, Stereochemistry, Analgesic Activity, and Opioid Receptor Binding Characteristics. Med. Chem.1995,38,3652-3659.
[48](a)王世玉,王普善.药物与中向体手册北京：化学工业出版社.2004,532-548.(b)陈绘如,肖国民4-哌啶酮类化合物的合成及其在医药领域中的应用.化工中间体,2005,(8)：1-4.
[49]冯亚青,史太昕,周立山等.N-甲基4-哌啶基甲醛的合成研究化学试剂,2001,23(4)：193-194.
[50]Yang, J. C.; Wang, N.; Yang, X. Extracts of Marasmims and Rosaceus L. ES, Piperdinone Derivatives and The Use as Antihypertensive Agents. WO 2005075423, 2005.
[51]For a review of the recent developments in asymmetric routes to substituted piperidines and piperidones, see:(a) Bailey, P. D.; Millwood, P. A.; Smith, P. D. Asymmetric Routes to Substituted Piperidines. Chem. Soc, Chem. Commun.1998,633-640. (b) Laschat, S.; Dickner, T._Stereoselective Synthesis of Piperidines Synthesis 2000,1781-1813. (c) Zhou, P.; Chen, B.-C.; Davis, F. A. Recent Advances in Asymmetric Reactions Using Sulfinimines N-sulfinyl Imines.Tetrahedron 2004,60,8003-8030. (d) Pearson, M. S. M.; Mathe-Allainmat, M.; Fargeas, V.; Lebreton, J._Recent Advances in The Total Synthesis of Piperidine Azasugars. Eur. Org. Chem.2005,11,2159-2191.
[52]Davis, F. A.; Chao, B.; Rao, A. Intramolecular Mannich Reaction in The Asymmetric Synthesis of Polysubstituted Piperidines:Concise Synthesis of the Dendrobate Alkaloid (+)-241D and Its C-4 Epimer. Org. Lett.2001,3,3169-3171.
[53]Ciblat, S.; Besse, P.; Canet, J.-L.; Troin, Y.; Veschambre, H.; Gelas, J.A practical Asymmetric Synthesis of 2,6-cis-disubstituted Piperidines.Tetrahedron:Asymmetry 1999,10,2225-2235.
[54]Ciblat, S.; Calinaud, P.; Canet, J.-L.; Troin, Y. J. A Simple Synthesis of (+) and (-)-alkaloid 241D and C-4 epimers.Chem. Soc., Perkin Trans.2000,1,353-357. (c) Glasson, S. R.; Canet, J.-L.; Troin, Y.A Rapid Stereoselective Access to Highly Substituted Piperidi- -nes.Tetrahedron Lett.2000,41,9797-9802. (d) Carbonnel, S.; Fayet, C.; Gelas, J.; Troi n, Y. Asymmetric Synthesis of C-6 Substituted Pipecolic Acid Derivatives. Tetrahedron Lett.2000,41,8293-8296. (e) Carbonnel, S.; Troin, Y. Heterocycles Stereoselective Syn thesis of C-6 Substituted Pipecolic Acid Derivatives. Formal Synthesis of (+)-Indolizidne 167B and (+)-Indolizidine 209D 2002,57, 1807-1830.
[55]Machetti, F.; Cordero, F. M.; De Sarlo, F.; Brandi, A.Practical Synthesis of Both Enanti omers of Protected 4-oxopipecolic Acid.Tetrahedron 2001,57,4995-4998.
[56]Ma, D.; Sun, H. A Simple and Stereospecfic Route to 2,6-Disubstituted 4-Hydroxypiperidnes. Synthesis of Dendrobate Alkaloid (+)-241D and Formal Synthesis of (-)-Indolizidine.Org. Lett.2000,2,2503-2505.
[57](a)Renault, O.; Guillon, J.; Dallemagne, P.; Rault, S.Efficient Synthesis of 2-aryl-6-methyl-2,3-dihydro-lH-pyridin-4-ones Tetrahedron Lett.2000,41,681-683. (b) Ma, D.; Sun, H. General Route to 2,4,5-Trisubstituted Piperidines from Enantiopure β-Amino Esters. Total Synthesis of Pseudodistomin B Triacetate and Pseudodistomin F. Org. Chem.2000,65,6009-6016.
[58]Weymann, M.; Pfrengle, W.; Schollmeyer, D.; Kunz, H. Enantioselective Syntheses of 2-Alkyl-,2,6-Dialkylpiperidines and Indolizidine Alkaloids Through Diastereoselective Mannich-Michael Reactions. Synthesis 1997,1151-1160.
[59]Kobayashi, S.; Kusakabe, K.; Ishitani, H. Chiral Catalyst Optimization Using Both Solid-Phase and Liquid-Phase Methods in Asymmetric Aza Diels-Alder Reactions. Org. Lett.2000,2,1225-1227.
[60]Kobayashi, S.; Komiyama, S.; Ishitani, H. A Molecular Chameleon:Chromophoric Sensing by a Self-Complexing Molecular Assembly Angew. Chem. Int. Ed.1998,37, 979-981.
[61](a) Sebesta, R.; Pizzuti, M.; Boersma, A. J.; Minnaard, A. J.; Feringa, B. L. Catalytic Enantioselective Conjugate Addition of Dialkylzinc Reagents to N-substituted-2,3-Dehydro 4-piperidones. Chem. Commun.2005,1711-1713. (b) Kranke, B.; Hebrault, D.; Schultz-Kukula, M.; Kunz, H. Arabinosylamine in Asymmetric Syntheses of Chiral Piperidine Alkaloids. Synlett 2004,671-674.
[62]Jack D. Brown, Michael A. Foley, and Daniel L. Comins A Highly Stereocontrolled, Four-Step Synthesis of (±)-Lasubine II. J. Am. Chem. Soc.1988,110,1445-1447.
[63]Syebesta, R.; Pizzuti, M. G.; Boersma, A. J.; Minnaard, A. J.; Feringa, B. L. Catalytic Enantioselective Conjugate Addition of Dialkylzinc Reagents to N-substituted-2,3-dehydro-4-piperidones. Chem. Commun.2005,1711-1713.
[64]Shintani, R.; Tokunaga, N.; Doi, H.; Hayashi, T. A New Entry of Nucleophiles in Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions:Addition of Organozinc Reagents for the Synthesis of 2-Aryl-4-piperidones. J. Am. Chem. Soc.2004,126, 6240-6241.
[65]Jagt, R. B. C.; de Vries, J. G.; Feringa, B. L.; Minnaard, A. Enantioselective Synthesis of 2-Aryl-4-piperidones via Rhodium/Phosphoramidite-Catalyzed Conjugate Addition of Arylboroxines. Org. Lett.2005,7,2433-2435.
[66]Gini, F.; Hessen, B.; Feringa, B. L.; Minnaard, A. Enantioselective Palladium-catalysed Conjugate Addition of Arylsiloxanes. Chem. Commun.2007,710-712.
[67]T. Chen, J.-J. Jiang, Q. Xu, M. Shi, Axially Chiral NHC-Pd(II) Complexes in the Oxidative Kinetic Resolution of Secondary Alcohols Using Molecular Oxygen as a Terminal Oxidant. Org. Lett.2007,9,865-868;
[68]Ma, G. N.; Zhang, T.; Shi, M. Letter Catalytic Enantioselective Arylation of N-Tosylarylimines with Arylboronic Acids Using C2-Symmetric Cationic N-Heterocyclic Carbene Pd2+Diaquo Complexes.Org. Lett.2009,11,875-878.
[69](a) Kozikowski, A. P.; Park, P.-U. Synthesis of Streptazolin:Use of the Aza-Ferrier Reaction in Conjunction with the INOC Process to Deliver a Unique but Sensitive Natural Product Org. Chem.1990,55,4668-4682. (b) Comins, D. L.; Chung, G.; Foley, M. A. Regio-and Stereoselective Addition of Nucleophiles to 1-Phenoxycarbonyl-2,3-dihy-dropyridinium Salts. Heterocycles 1994,37,1121-1140.
[70]Nakaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.; Miyaura, N. Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl-and Alkenylboronic Acids to Enones. J. Am. Chem. Soc.1998,120,5579-5580.
[71](a) Denmark S. E; Amishiro N. Palladium-catalyzed conjugate addition of organosiloxanes to alpha,beta-unsaturated carbonyl compounds and nitroalkenes. J. org. chem.2003,68,6997-7003. (b) Nishikata, T.; Yamamoto, Y.; Miyaura, N.1,4-Addition of arylsiloxanes to enones catalyzed by dicationic palladium(II) complexes in aqueous media. Chem. Lett.2003,32,752-753.
[72](a) Yao, S.; Meng, J. C.; Siuzdak, G.; Finn, M. G.; New Catalysts for the Asymmetric Hydrosilylation of Ketones Discovered by Mass Spectrometry Screening J. Org. Chem. 2003,68,2540-2546. (b) Hu, X.; Chen, H.; Dai, H.; Zheng, Z. Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine Tetrahedron Asymmetry 2003, 14,3415-3421. (c) Tao, B.; Fu, G. C. Application of aNew Family of P,N Ligands to the Highly Enantioselective Hydrosilylation of Aryl Alkyl and Dialkyl Ketones Angew. Chem. Int. Ed.2002,41,3892-3894. (d) Nishibayashi, Y.; Segawa, K.; Ohe, K.; Uemura, S. Chiral Oxazolinyl ferrocene-Phosphine Hybrid Ligand for the Asymmetric Hydrosilylation of Ketones Organometallics 1995,14,5486-5487. (e) Coyne, A. G.; Guiry, P. J. Rhodium-catalysed asymmetric hydrosilylation of ketones using HETPHOX ligands Tetrahedron Lett.2007,48,747-750.
[73]H. Nishiyama, K. Itoh in Catalytic Asymmetric Synthesis,2nd ed. (Ed.:I. Ojima), Wiley-VCH, Weinheim,2000, pp.111-144.
[74](a) Comprehensive Handbook on Hydrosilylation (Ed.:B. Marciniec), Pergamon Press, Oxford,1992. (b)Hydrosilylation:A Comprehensive Review on Recent Advances (Ed.: B. Marciniec), Springer, Heidelberg,2009.
[75](a) E.N. Jacobsen, A. Pfaltz, H. Yamamoto, Comprehensive Asymmetric Catalysis, vol. 1, Springer, Berlin,1999.
[76](a) Lappert, M. F. In Transition Metal Chemistry, Eds:Mηller, A.; Diemann, E., Verlag Chemie, Weinheim,1981, p.287.
[77]Herrmann, W. A.; Baskakov, D.; Herdtweck, E.; Hoffmann, S. D.; Bunlaksananusorn, T.; Rampf, F.; Rodefeld, L. Chiral N-Heterocyclic Carbene Ligands Derived from 2,2'-Bipiperidine and Partially Reduced Biisoquinoline:Rhodium and Iridium Complexes in Asymmetric Catalysis. Organometallics 2006,25,2449-2459.
[78]Faller, J. W.; Fontaine, P. P. Stereodynamics and Asymmetric Hydrosilylation with Chiral Rhodium Complexes Containing a Monodentate N-Heterocyclic Carbene. Organometallics 2006,25,5887-5893.
[79]Enders, D.; Gielen, H.; Breuer, K. Catalytic Asymmetric Hydrosilylation with (triazolinylidene)Rhodium Complexes Containing an Axis of Chirality. Tetrahedron: Asymmetry 1997,8,3571-3574.
[80](a) Gade, L. H.; Cesar, V.; Bellemin-Laponnaz, S. A Modular Assembly of Chiral Oxazolinylcarbene-Rhodium Complexes:Efficient Phosphane-Free Catalysts for the Asymmetric Hydrosilylation of Dialkyl Ketones. Angew. Chem. Int. Ed.2004,43, 1014-1017. (b) Cesar, V.; Bellemin-Laponnaz, S.; Wadepohl, H.; Gade, L. H. Designing theSearch Pathwayin the Development of a New Class of Highly Efficient Stereoselective Hydrosilylation Catalysts. Chem. Eur.J.2005,11,2862-2873.
[81]Yuan, Y.; Raabe, G.; Bolm, C. Novel Rhodium Complexes with Ferrocene-based N-heterocylic Carbenes:Synthesis, Structure and Catalysis. J. Organomet. Chem.2005, 690,5747.
[82]Ros, A.; Alcarazo, M.; Iglesias-Siguenza, J.; Diez, E.; Alvarez, E.; Fernandez, R.; Lassaletta, J. M. Stereoselective Synthesis of Rhodium(I) 4-(Dialkylamino) Triazol-5-ylidene Complexes. Organometallics 2008,27,4555
[83]Chianese, A. R.; Crabtree, R. H. Axially Chiral Bidentate N-Heterocyclic Carbene Ligands Derived from BIN AM:Rhodium and Iridium Complexes in Asymmetric Ketone Hydrosilylation. Organometallics 2005,24,4432-4436.
[84]Song, C.; Ma, C.; Ma, Y.; Feng, W.; Ma, S.; Chai, Q.; Andrus, M. B. Bis-paracyclophane N-heterocyclic Carbene-Ruthenium Catalyzed Asymmetric Ketone Hydrosilylation. Tetrahedron Lett.2005,46,3241-3244.
[85](a) Mori, K. Synthesis of Optically Active Pheromones.Tetrahedron 1989,45,3233. (b) Girard, A.; Greck, C.; Ferroud, D.; Genet, J. P. Syntheses of the Syn and Anti a-amino-β-hydroxy Acids of Vancomycin:(2S,3R) and (2R,3R) P-chloro-3-hydroxytyrosines.Tetrahedron Lett.1996,37,7967. (c) Ali, I. S.; Sudalai, A. Pd-Catalyzed Kinetic Resolution of Benzylic Alcohols:a Practical Synthesis of (R)-tomoxetine and (S)-fluoxetine hydrochlorides.Tetrahedron Lett.2002,43,5435. (d) Wirth, D. D.; Miller, M. S.; Boini, S. K.; Koenig, T. M. Identification and Comparison of Impurities in Fluoxetine Hydrochloride Synthesized by Seven Different Routes. Org. Process Res. Dev.2000,4,513. (e) Hodgetts, K. Approaches to 2-substituted chroman-4-ones:Synthesis of (-)-pinostrobin. J. Tetrahedron Lett.2001,42,3763.
[86](a) Tang, W.; Zhang, X. New Chiral Phosphorus Ligands for Enantioselective Hydrogenation.Chem. Rev.2003,103,3029. (b) McCarthy, M.; Guiry, P. Axially Chiral Bidentate Ligands in Asymmetric Catalysis. Tetrahedron 2001,57,3809. (c) Catalytic Asymmetric Synthesis; Ojima, I. Ed.; Wiley-VCH:Weinheim, Germany,2000. (d) Comprehensive Asymmetric Catalysis; Jacobsen, E. N.; Pfalts, A.; Yamamoto, H. Eds.; Springer:Berlin, Germany,1999.
[87](a) Davies, H. G.; Green, R. H.; Kelly, D. R.; Roberts, S.. In Biotransformations in Preparative Organic Chemistry. The Use of Isolated Enzymes and Whole Cell Systems in Synthesis; Academic Press:London,1989 (Chapter 3). (b) Rodriguez, S.; Kayser, M. M.; Stewart, J. D. Highly Stereoselective Reagents for β-Keto Ester Reductions by Genetic Engineering of Baker's Yeast J. Am. Chem. Soc.2001,123,1547-1555. (c) Buque, E. M.; Chin-Joe, I.; Straathof, A. J. J.; Jongejan, J. A.; Heijnen, J. Immobilization Affects the Rate and Enantioselectivity of 3-oxo Ester Reduction by Baker's Yeast. J. Enzyme Microb. Technol.2002,31,656.
[88](a) Duthaler, R.O.; Herold, P.; Lottenbach, W.; Oertle, K.; Riediker, M. Enantioselective Aldol Reaction of Tert-Butyl Acetate Using Titanium-Carbohydrate Complexes Angew. Chem. Int. Ed. Engl.1989,28,495. (b) Mioskowski, C.; Solladie, G. Syntheses Asymetriques De β-hydroxyacides Par condensation d'anions Enolates d'esters a-sulfinyle Chiraux Sur des Composes Carbonyles.Tetrahedron 1979,36,227. (c) Meyers, A. I.; Knaus, G. Synthesis via oxazolines. VI. An asymmetric Synthesis of P-hydroxy and P-methoxy Alkanoic acids.Tetrahedron Lett.1974,15,1333.
[89]Ocampo R, Dolbier W R. The Reformatsky reaction in organic synthesis Recent advances. Tetrahedron 2004,60,9325-9374
[90](a) Azerad, R.; Buisson, D. In Microbial Reagents in Organic Synthesis; Servi, S., Ed.; Kluwer Academic Publishers:Dordecht, The Netherlands,1992; pp 421. (b) Nakamura, K.; Fuji, M.; Ida, Y. Stereoinversion of Arylethanols by Geotrichum Candidum. Tetrahedron:Asymmetry 2001,12,3147. (c) Padhi, S. K.; Chadha, A. Deracemisation of Aromatic β-Hydroxy Esters Using Immobilised Whole Cells of Candida Parapsilosis ATCC 7330 and Determination of Absolute Configuration by 1H NMR.Tetrahedron: Asymmetry 2005,16,2790.
[91]Xu, C.; Yuan,C. Candida Rugosa Lipase-catalyzed Kinetic Resolution of β-hydroxy-β-arylpropi Onates and δ-hydroxy-δ-aryl-β-oxo-pentanoates. Tetrahedron 2005,61,2169.
[92]Cesar, V.; Bellemin-Laponnaz, S.; Wadepohl, H.; Gade, L. H. Designing the "Search Pathway" in the Development of a New Class of Highly Efficient Stereoselective Hydrosilylation Catalysts. Chem. Eur.2005,11,2862.
[93]Tsuji, J. Palladium reagents and catalysts[C]. New York:J. Wiley,2004.
[94](a) Zhou, J.; Fu, G. C. Palladium-Catalyzed Negishi Cross-Coupling Reactions of Unactivated Alkyl Iodides, Bromides, Chlorides, and Tosylates J. Am. Chem. Soc.2003, 125,12527-12530. (b) Lee, H.-M.; Nolan, S. P. Efficient Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyl-or Vinyltrimethoxysilane Mediated by a Palladium/Imidazolium Chloride System Org. Lett.2000,2,2053-2055.
[95]Herrmann, W. A. N-Heterocyclic carbenes:A new concept in organometallic catalysis. Angew. Chem. Int. Ed.2002,41,1290-1309.
[96]Miyaura, N.; Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds Chem. Rev.1995,95,2457-2483.
[97](a) Heck, R. F. Palladium Reagents in Organic Syntheses; Academic Press:New York, 1985. (b) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. In Principles and Applications of Organotransition Metal Chemistry; University Science:Mill Valley, CA, 1987. (c) Diederich, F., Stang, P. J. Metal-Catalyzed Cross-Coupling Reactions; Wiley-VCH:Weinheim,1998.
[98]Herrmann, W. A.; Reisinger, C. P.; Spiegler, M. Chelating N-heterocyclic carbene ligands in palladium-catalyzed Heck-type reactions. J. Organomet. Chem.1998,557,93-96.
[99](a) Zhang, C; Huang, J.; Trudell, M. L.; Nolan, S. P. Palladium-imidazol-2-ylidene complexes as catalysts for facile and efficient Suzuki cross-coupling reactions of aryl chlorides with arylboronic acids. J. Org. Chem.1999,64,3804-3805. (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.; Trudell, M. L.; Nolan, S. P. Suzuki-Miyaura cross-coupling reactions mediated by palladium/imidazolium salt systems. Organometallics 2002,21,2866-2873.
[100](a) Navarro, O.; Marion, N.; Mei, J.; Nolan, S. P. Rapid room temperature Buchwald-Hartwig and Suzuki-Miyaura couplings of heteroaromatic compounds employing low catalyst loadings. Chem. Eur. J.2006,12,5142-5148. (b) Singh, R.; Viciu, M. S.; Kramareva, N.; Navarro, O.; Nolan, S. P. Simple (Imidazol-2-ylidene)-Pd-acetate complexes as effective precatalysts for sterically hindered Suzuki-Miyaura couplings. Org. Lett.2005,7,1829-1832.
[101](a) Cabri, W.; Candiani, I. Recent Developments and New Perspectives in the Heck Reaction Acc.Chem. Res.1995,28,2-7. (b) Dounay, A. B.; Overman, L. E. The Asymmetric Intramolecular Heck Reaction in Natural Product Total Synthesis Chem. Rev.2003,103,2945-2964.
[102](a) Shibasaki, M.; Boden, C. O. J.; Kojima, A. The asymmetric Heck reaction Tetrahedron 1997,53,7371-7395. (b) Beletskaya, I. P.; Cheprakov, A. V. The Heck Reaction as a Sharpening Stone of Palladium Catalysis Chem. Rev.2000,100, 3009-3066. (c) Whitcombe, N. J.; Hii, K. K.; Gibson, S. E. Advances in the Heck chemistry of aryl bromides and chlorides Tetrahedron 2001,57,7449-7476. (d) Littke, A. F.; Fu, G. C. Palladium-Catalyzed Coupling Reactions of Aryl Chlorides Angew. Chem., Int. Ed.2002,41,4176-4211. (e) Alonso, F.; Beletskaya, I. P.; Yus, M. Non-conventional methodologies for transition-metal catalysed carbon-carbon coupling: a criticalo verview.Part 1:The Heck reaction Tetrahedron 2005,61,11771-11835.
[103](a) Ikeda, Y.; Nakamura, T.; Yorimitsu, H.; Oshima, K Cobalt-Catalyzed Heck-Type Reaction of Alkyl Halides with Styrenes. J. Am. Chem. Soc.2002,124,6514-6515. (b) Fujioka, T.; Nakamura, T.; Yorimitsu, H.; Oshima, K. Cobalt-Catalyzed Intramolecular Heck-Type Reaction of 6-Halo-1-hexene Derivatives Org. Lett.2002,4,2257-2259.
[104](a) Iyer, S.; Ramesh, C.; Sarkar, A.; Wadgaonkar, P. P. The Vinylation of Aryl and Vinyl Halides Catalyzed by Copper Salts Tetrahedron Lett.1997,38,8113-8116.
[105](a) Boldrini, G. P.; Savola, D.; Tagllavini, E.; Trombini, C.; Umanironchi, A. Nickel-catalyzed coupling of activated alkenes with organic halides J. Organomet. Chem. 1986,301,62-64. (b) Lebedev, S. A.; Lopatina, V. S.; Petrov, E. S.; Beletskaya, I. P. Condensation of organic bromides with vinyl compounds catalysed by nickel complexes in the presence of zinc J. Organomet. Chem.1988,344,253-259. (c) Kong, K.-C.; Cheng, C.-H. Synthesis of spiro dienones from internal acetylene and cyclic 3-iodo enones in the presence of nickel bromide and zinc powder Organometallics 1992,11, 1972. (d) Sustmann, S.; Hopp, P.; Holl, P. Reactions of organic halides with olefins under Nio-catalysis. Formal addition of hydrocarbons to CC-double bonds Tetrahedron Lett.1989,30,689.
[106]Eckhardt, M.; Fu, G. C. The first applications of carbene ligands in cross-couplings of alkyl electrophiles:Sonogashira reactions of unactivated alkyl bromides and iodides. J. Am. Chem. Soc.2003,125,13642-13643.
[2]Wanzlick, H. W.; Schnherr, H. J. Chemistry of Nucleophilic Carbene XIV. Direct Synthesis of a Mercury Salt-Carbene Complex. Angew. Chem. Int. Ed. Engl.1968,7, 141-142.
[3](a) Arduengo, A. J. Ⅲ.; Harlow, R. L.; Kline, M. A Stable Crystsline Carbene. J. Am. Chem. Soc.1991,113,361-363. (b) Arduengo, A. J. Ⅲ.; Kline, M.; Calabress, J. C. Synthesis of a Reverse Ylide from a Nucleophilic Carbene. J. Am. Chem. Soc.1991,113, 9704-9705. (c) Arduengo, A. J. Ⅲ.; Krafczyk, R.; Schmutzler, R. Imidazolylidenes, Imidazolinylidenes and Imidazolidines. Tetrahedron 1999,55,14523-14534.
[4]Herrmann, W. A.; Elison, M.; Fischer, J.; Kocher, C.; Artus, G. R. Metal Complexes of N-Heterocyclic Carbenes-A New Structural Principle for Catalysts in Homogeneous Catalysis J. Angew. Chem., Int. Ed. Engl.1995,34, 2371-2374.
[5]Teles, J. H.; Melder, J.-P.; Ebel, K.; Schneider, R.; Gehrer, E.; Harder, W.; Brode, S.; Enders, D.; Breuer, K.; Raabe, G. New Mechanistic Proposal for Some Heptamolybdate-Ion-Catalyzed Isomerizations. Helv. Chim. Acta.1996,79,61-83.
[6]Kiiciikbay, H.; C, etinkaya, B.; Guesmi, S.; Dixneuf, P. H. New (Carbene) RutheniumArene Complexes:Preparation and Uses in Catalytic Synthesis of Furans. Organometallics 1996,15,2434-2439.
[7](a) Herrmann, W. A. N-Heterocyclic Carbenes:A New Concept in Organometallic Catalysis. Angew. Chem., Int. Ed.2002,41,1290-1309. (b) Herrmann, W. A.; Kocher, C. N-Heterocyclic Carbenes. Angew. Chem., Int. Ed. Engl.1997,36,2162-2187.
[8]Crabtree, R. H. NHC Ligands Versus Cyclopentadienyls and Phosphines as Spectator Ligands in Organometallic Catalysis. J. Organomet. Chem.2005,690,5451-5457.
[9](a) Herrmann, W. A. N-Heterocyclic Carbenes:A new Concept in Organometallic Catalysts. Angew. Chem. Int. Ed.2002,40,1290-1309. (b) Despagnet-Ayoub, E.; Grubbs, R. H. A Stable Four-Membered N-Heterocyclic Carbene. J. Am. Chem. Soc.2004,126, 10198-10199. (c) Despagnet-Ayoub, E.; Grubbs, R. H. A Ruthenium Olefin Metathesis Catalyst with a Four-membered N-heterocyclic Carbene Ligand. Organometallics 2005, 24,338-340. (d) Alder, R. W.; Blake, M. E.; Bortolotti, C.; Bufali, S.; Butts, C. P.; Linehan, E.; Oliva, J. M.; Orpen, A. G; Quayle, M. J. Complexation of Stable Carbenes with Alkali Metals. Chem. Commun.1999,241-242. (e) Bazinet, P.; Yap, G P. A.; Richeson, D. S. Constructing a Stable Carbene with a Novel Topology and Electronic Framework. J. Am. Chem. Soc.2003,125,13314-13315.
[10](a) Enders, D.; Niemeier,O.; Henseler, A. Organocatalysis by N-Heterocyclic Carbenes. Chem. Rev.2007,107,5606. (b) Marion, N.; Diez-Gonzalez, S.; Nolan, S. P. N-Heterocyclic Carbenes as Organocatalysts. Angew. Chem. Int. Ed.2007,46,2988. (c) Hahn, F. E.; Jahnke, M. C. Heterocyclic Carbenes:Synthesis and Coordination Chemistry. Angew. Chem. Int. Ed.2008,47,3122. (d) Liddle, S. T.; Edworthy, I. S.; Arnold, P. L. Anionic Tethered N-heterocyclic Carbene Chemistry. Chem. Soc. Rev. 2007,36,1732.
[11]Breslow, R. On the Mechanism of Thiamine Action IV Evidence from Studies on Model Systems. J. Am. Chem. Soc.1958,80,3719.
[12]Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H. The First Asymmetric Intramolecular Stetter Reaction Preliminary Communication. Helv. Chim. Acta.1996,79,1899-1902.
[13]Enders, D.; Kallfass, U. An Efficient Nucleophilic Carbene Catalyst for the Asymmetric Benzoin Condensation. Angew. Chem. Int. Ed.2002,41,1743-1745.
[14]Burstein, C.; Glorius, R. Organocatalyzed Conjugate Umpolung of unsaturated Aldehydes for the Synthesis of y-butyrolactones. Angew. Chem. Int. Ed.2004,43, 6205-6208.
[15]Suzuki, Y.; Toyota, T.; Imada, F.; Sato, M.; Miyashita, A. Nucleophilic Acylation of Arylfluorides Catalyzed by Imidazolidenyl Carbene. Chem. Commun.2003,1314-1315.
[16]Connor, E. F.; Nyce, G. W.; Myers, M.; Mock, A; Hedrick, J. L. First Example of N-Heterocyclic Carbenes as Catalysts for Living Polymerization:Organocatalytic Ring-Opening Polymerization of Cyclic Esters. J. Am. Chem. Soc.2002,124,914.
[17](a)Herrmannn, W. A.; Elison, M.; Fischer, J.; Kocher, C.; Artus, G. R. J. Metal Complexes of N-heterocyclic Carbenes:A New Structural Principle for Catalysts in Homogeneous Catalysis. Angew. Chem. Int. Ed. Engl.1995,34,2371-2374. (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.; Trudell, M. L.; Nolan, S. P. Suzuki-Miyaura Cross-Coupling Reactions Mediated by Palladium/Imidazolium Salt Systems Organometallics 2002,21,2866-2873. (c) Vargas, V. C.; Rubio, R. J.; Hollis, T. K.; Salcido, M. E. Efficient Route to 1,3-Di-N-imidazolylbenzene. A Comparison of Monodentate vs Bidentate Carbenes in Pd-Catalyzed Cross Coupling Org. Lett.2003,5, 4847-4849. (d) Navarro, O.; Kelly, R. A.; Nolan, S. P. A General Method for the Suzuki-Miyaura Cross-Coupling of Sterically Hindered Aryl Chlorides:Synthesis of Di-and Tri-ortho-substituted Biaryls in 2-Propanol at Room Temperature J. Am. Chem. Soc.2003,125,16194-16195. (e) Marion, N.; Nolan, S. P. Acc. Chem. Res.2008,41, 1440-1449; (f) Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G. Palladium Complexes of N-Heterocyclic Carbenes as Catalysts for Cross-Coupling Reactions A Synthetic Chemist's Perspective Angew. Chem., Int. Ed.2007,46,2768-2813. (g) Navarro, O.; Kelly, R. A.; Nolan, S. P. A General Method for the Suzuki-Miyaura Cross-Coupling of Sterically Hindered Aryl Chlorides:Synthesis of Di-and Tri-ortho-substituted Biaryls in 2-Propanol at Room Temperature J. Am. Chem. Soc.2003,125,16194-16195 (h) Altenhoff, G.; Goddard, R.; Lehmann, C. W.; Glorius, F. Sterically Demanding, Bioxazoline-Derived N-Heterocyclic Carbene Ligands with Restricted Flexibility for Catalysis J. Am. Chem. Soc.2004,126,15195-15201. (i) Marion, N.; Navarro, O.; Mei, J.; Stevens, E. D.; Scott, N. M.; Nolan, S. P. Modified (NHC)Pd(allyl)Cl (NHC= N-Heterocyclic Carbene) Complexes for Room-Temperature Suzuki-Miyaura and Buchwald-Hartwig Reactions J. Am. Chem. Soc.2006,128,4101-4111. (j) Percec, V.; Golding, G. M.; Smidrkal, J.; Weichold, O. NiCl2(dppe)-Catalyzed Cross-Coupling of Aryl Mesylates, Arenesulfonates, and Halides with Arylboronic Acids J. Org. Chem. 2004,69,3447-3452. (k) Blakey, S. B.; MacMillan, D. W. C. The First Suzuki Cross-Couplings of Aryltrimethylammonium Salts J. Am. Chem. Soc.2003,125, 6046-6047. (1) Liu, J.; Robins, M. J. zoles as Suzuki Cross-Coupling Leaving Groups: Syntheses of 6-Arylpurine 2'-Deoxynucleosides and Nucleosides from 6-(Imidazol-1-yl)-and 6-(1,2,4-Triazol-4-yl)purine Derivativesl Org. Lett.2004,6, 3421-3423. (m) N-Heterocyclic Carbenes in Synthesis; Nolan, S. P., Ed.; Wiley-VCH: Weinheim,2006. (n) Herrmann, W. A. N-Heterocyclic Carbenes:A New Concept in Organometallic Catalysis Angew. Chem., Int. Ed.2002,41,1290. (m) Bohm, V. P. W.; Weskamp, T.; Gsto"ttmayr, C. W. K.; Herrmann, W. A. Nickel-Catalyzed Cross-Coupling of Aryl Chlorides with Aryl Grignard Reagents Angew. Chem., Int. Ed. 2000,39,1602-1604. (o) Bohm, V. P.W.; Gstottmayr, C. W. K.; Weskamp, T.; Herrmann, W. A. Catalytic C-C Bond Formation through Selective Activation of C-F Bonds Angew. Chem., Int. Ed.2001,40,3387-3389. (p) Kiyofumi, I.; Jun-ichi, K.; Takao, S.; Kou, K. Catalytic Activities of a Bis(carbene)-Derived Nickel(II)-Pincer Complex in Kumada-Tamao-Corriu and Suzuki-Miyaura Coupling Reactions for the Synthesis of Biaryl Compounds Synthesis 2007,2853-2861. (q) Matsubara, K.; Ueno, K.; Shibata, Y. Synthesis and Structures of Nickel Halide Complexes Bearing Mono-and Bis-coordinated N-Heterocyclic Carbene Ligands, Catalyzing Grignard Cross-Coupling Reactions Organometallics 2006,25,3422-3427. (r) Rudolph, A.; Lautens, M. Secondary Alkyl Halides in Transition-Metal-Catalyzed Cross-Coupling Reactions Angew. Chem., Int. Ed.2009,48,2656-2670. (s) Glorius, F. Asymmetric Cross-Coupling of Non-Activated Secondary Alkyl Halides Angew. Chem., Int. Ed. 2008,47,8347-8349. (t) Frisch, A. C.; Beller, M. Catalysts for Cross-Coupling Reactions with Non-activated Alkyl Halides Angew. Chem., Int. Ed.2005,44,674-688. (u) Bedford, R. B.; Betham, M.; Bruce, D. W.; Danopoulos, A. A.; Frost, R. M.; Hird, M. Iron-Phosphine,-Phosphite,-Arsine, and-Carbene Catalysts for the Coupling of Primary and Secondary Alkyl Halides with Aryl Grignard Reagents J. Org. Chem.2006, 71,1104-1110. (v) Hatakeyama, T.; Nakamura, M. Iron-Catalyzed Selective Biaryl Coupling:Remarkable Suppression of Homocoupling by the Fluoride Anion J. Am. Chem. Soc.2007,129,9844-9845. (w) Yamagami, T.; Shintani, R.; Shirakawa, E.; Hayashi, T. Iron-Catalyzed Arylmagnesiation of Aryl(alkyl)acetylenes in the Presence of an N-Heterocyclic Carbene Ligand Org. Lett.2007,9,1045-1048.
[18](a) Herrmann, W. A.; Goossen, L. T.; Kocher, C.; Artus, G. R. J. Chiral heterocyclic carbenes in asymmetric homogeneous catalysis. Angew. Chem. Int. Ed. Engl.1996,35, 2805-2807. (b) Gade, L. H.; Cesar, V.; Bellemin-Laponnaz, S. A Modular Assembly of Chiral Oxazolinylcarbene-Rhodium Complexes:Efficient Phosphane-Free Catalysts for the Asymmetric Hydrosilylation of Dialkyl Ketones Angew. Chem., Int. Ed.2004,43, 1014-1017. (c) Enders, D.; Gielen, H. Synthesis of Chiral Triazolinylidene and Imidazolinylidene Transition metal Complexes and First Application in Asymmetric Catalysis. J. Organomet. Chem.2001,617-618,70-80. (d) Schneider, N.; Finger, M.; Haferkemper, C.; Bellemin-Laponnaz, S.; Hofmann, P.; Gade, L. H. Metal Silylenes Generated by Double Silicon-Hydrogen Activation:Key Intermediates in the Rhodium-Catalyzed Hydrosilylation of Ketones Angew. Chem., Int. Ed.2009,48, 1609-1613. (e) Duan, W.-L.; Shi, M.; Rong, G.-B. Synthesis of Novel Axially Chiral Rh-NHC Complexes Derived from BINAM and Application in the Enantioselective Hydrosilylation of Methyl Ketones. Chem. Commun.2003,2916-2917. (f) Yuan, Y.; Raabe, G.; Bolm, C. Novel rhodium complexes with ferrocene-based N-heterocylic carbenes:Synthesis, structure and catalysis J. Organomet. Chem.2005,690,5747-5752. (g) Faller, J. W.; Fontaine, P. P. Stereodynamics and Asymmetric Hydrosilylation with Chiral Rhodium Complexes Containing a Monodentate N-Heterocyclic Carbene Organometallics 2006,25,5887-5893. (h) Nonnenmacher, M.; Kunz, D.; Rominger, F. Synthesis and Catalytic Properties of Rhodium(I) and Copper(I) Complexes Bearing Dipyrido-Annulated N-Heterocyclic Carbene Ligands Organometallics 2008,27, 1561-1568. (i) Ros, A.; Alcazaro, M.; Iglesias-Siguenza, J.; Diez, E.; Alvarez, E.; Ferna'ndez, R.; Lassaletta, J. M. Stereoselective Synthesis of Rhodium(I) 4-(Dialkylamino)triazol-5-ylidene Complexes Organometallics 2008,27,4555-4564. (j) Jime'nez, M. V.; Perez-Torrente, J. J.; Bartolome, M. I.; Gierz, V.; Lahoz, F. J.; Oro, L. A. Rhodium(I) Complexes with Hemilabile N-Heterocyclic Carbenes:Efficient Alkyne Hydrosilylation Catalysts Organometallics 2008,27,224-234. (k) Hu, J. J.; Li, F.; Hor, T. S. A. Novel Pt(II) Mono-and Biscarbene Complexes:Synthesis, Structural Characterization and Application in Hydrosilylation Catalysis Organometallics 2009,28, 1212-1220. (1) Poyatos, M.; Maisse-Franc.ois, A.; Bellemin-Laponnaz, S.; Gade, L. H. Coordination Chemistry of a Modular N,C-Chelating Oxazole-Carbene Ligand and Its Applications in Hydrosilylation Catalysis Organometallics 2006,25,2634-2641. (m) De Bo, G.; Berthon-Gelloz, G.; Tinant, B.; Marko, I. E. Hydrosilylation of Alkynes Mediated by N-Heterocyclic Carbene Platinum(0) Complexes Organometallics 2006,25, 1881-1890. (n) Berthon-Gelloz, G.; Schumers, J.-M.; De Bo, G.; Marko, I. E. Highly β-(E)-Selective Hydrosilylation of Terminal and Internal Alkynes Catalyzed by a (IPr)Pt(diene) Complex J.Org. Chem.2008,73,4190-4197.
[19](a) Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Synthesis of Cyclic Polybutadiene via Ring-Opening Metathesis Polymerization:The Importance of Removing Trace Linear Contaminants J. Am. Chem. Soc.2003,125,8424-8425. (b) Boydston, A. J.; Xia, Y.; Kornfield, J. A.; Gorodetskaya, I. A.; Grubbs, R. H. Cyclic Ruthenium-Alkylidene Catalysts for Ring-Expansion Metathesis Polymerization J. Am. Chem. Soc.2008,130,
12775-12782. (c) Occhipinti, G.; Bj(?)rsvik, H. R.; Tomroos, K. W.; Furstner, A. Jensen, V. R. The First Imidazolium-Substituted Metal Alkylidene Organometallics 2007,26,4383-4385. (d) Yun, S. Y.; Kim, M.; Lee, D.; Wink, D. J. Structure and Reactivity of Alkynyl Ruthenium Alkylidenes J. Am. Chem. Soc.2009,131,24-25. (e) Bolton, S. L.; Williams, J. E.; Sponsler, M. B. Stabilization of (Trialkylphosphine)ruthenium Alkylidene Metathesis Catalysts using Phosphine Exchange Organometallics 2007,26,2485-2487. (f) Rix, D.; Caijo, F.; Laurent, I.; Boeda, F.; Clavier, H.; Nolan, S. P.; Mauduit, M. Aminocarbonyl Group Containing Hoveyda-Grubbs-Type Complexes:Synthesis and Activity in Olefin Metathesis Transformations J.Org. Chem.2008,73,4225-4228.
[20](a) Tsarevsky, N. V.; Matyjaszewski, K. "Green" Atom Transfer Radical Polymerization:From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials Chem. Rev.2007,107,2270-2299. (b) McGuinness, D. S.; Gibson, V. C.; Steed, J. W. Bis(carbene)pyridine Complexes of the Early to Middle Transition Metals:Survey of Ethylene Oligomerization and Polymerization Capability Organometallics 2004,23,6288-6292. (c) Danopoulos, A. A.; Tsoureas, N.; Wright, J. A.; Light, M. E. N-Heterocyclic Pincer Dicarbene Complexes of Iron(II):C-2 and C-5 Metalated Carbenes on the Same Metal Center Organometallics 2004,23,166-168. (d) Chen, M.-Z.; Sun, H.-M.; Li, W.-F.; Wang, Z.-G.; Shen, Q.; Zhang, Y. Synthesis, structure of functionalized N-heterocyclic carbene complexes of Fe(II) and their catalytic activity for ring-opening polymerization of ε-caprolactone J. Organomet. Chem.2006, 691,2489-2494. (e) Csabai, P.; Joo, F.; Trzeciak, A. M.; Ziolkowski, J. J. Catalytic activity of a half-sandwich Ru(Ⅱ)-N-heterocyclic carbene complex in the oligomerization of alkynes J. Organomet. Chem.2006,691,3371-3376. (f) Zhang, Y.; Wang, D.; Wurst, K.; Buchmeiser, M. R. Polymerization of phenylacetylene by novel Rh (I)-, Ir (I)-and Ru (Ⅳ) 1,3-R2-3,4,5,6-tetrahydropyrimidin-2-ylidenes(R= mesityl, 2-propyl):Influence of structure on activity and polymer structure J. Organomet. Chem. 2005,690,5728-5735. (g) Becker, E.; Stingl, V.; Dazinger, G.; Puchberger, M.; Mereiter, K.; Kirchner, K. Facile Migratory Insertion of a N-Heterocyclic Carbene into a Ruthenium-Carbon Double Bond:A New Type of Reaction of a NHC Ligand J. Am. Chem. Soc.2006,128,6572-6573. (h) Becker, E.; Stingl, V.; Mereiter, K.; Kirchner, K. Formation of a Half-Sandwich Triscarbene Ruthenium Complex:Oxidative Coupling of 2,7-Nonadiyne Mediated by [RuCp(IPri)(CH3CN)2]+(IPri= 1,3-bis(2,6-diisopropylphenyl) imidazol-2-ylidene) Organometallics 2006,25, 4166-4169.
[21](a) Poyatos, M.; Maisse-Francois, A.; Bellemin-Laponnaz, S.; Peris, E.; Gade, L. H.Synthesis and structural chemistry of arene-ruthenium half-sandwich complexes bearing an oxazolinyl-carbene ligand J. Organomet. Chem.2006,691,2713-2720. (b) Cheng, Y.; Sun, J.-F.; Yang, H.-L.; Xu, H.-J.; Li, Y.-Z.; Chen, X.-T.; Xue, Z.-L Syntheses, Structures, and Catalytic Properties of Ruthenium(II) Nitrosyl Complexes with Pyridine-Functionalized N-Heterocyclic Carbenes Organometallics 2009,28, 819-823. (c) Enthaler, S.; Jackstell, R.; Hagemann, B.; Junge, K.; Erre, G.; Beller, M. Efficient transfer hydrogenation of ketones in the presence of ruthenium N-heterocyclic carbene catalysts J. Organomet. Chem.2006,691,4652-659. (d) Zeng, F.; Yu, Z. Ruthenium(II) Complexes Bearing a Pyridyl-Supported Pyrazolyl-N-Heterocyclic Carbene (NNC) Ligand and Their Catalytic Activity in the Transfer Hydrogenation of Ketones Organometallics 2008,27,6025-6028. (e) Lee, H. M.; Smith, D. C., Jr.; Ho, Z.; Stevens, E. D.; Yi, C. S.; Nolan, S. P. Catalytic Hydrogenation of Alkenes by the Ruthenium-Carbene Complex HRu(CO)Cl(PCy3)(IMes) (IMes= Bis(1,3-(2,4,6-trimethylphenyl)imidazol-2-ylidene) Organometallics 2001,20,794-797. (f) Banti, D.; Mol, J. C. Degradation of the ruthenium-based metathesis catalyst [RuCl2(=CHPh)(H2IPr)(PCy3)] with primary alcohols J. Organomet. Chem.2004,689, 3113-3116. (g) Dharmasena, U. L.; Foucault, H.; dos Santos, E. N.; Fogg, D. E.; Nolan, S. P. N-Heterocyclic Carbenes as Activating Ligands for Hydrogenation and Isomerization of Unactivated Olefins Organometallics 2005,24,1056-1058. (h) Burling, S.; Paine, B. M.; Nama, D.; Brown, V. S.; Mahon, M. F.; Prior, T. J.; Pregosin, P. S.; Whittlesey, M. K.; Williams, J. M. J. C-H Activation Reactions of Ruthenium N-Heterocyclic Carbene Complexes:Application in a Catalytic Tandem Reaction Involving C-C Bond Formation from Alcohols J. Am. Chem. Soc.2007,129, 1987-1995. (i) Jazzar, R. F. R.; Macgregor, S. A.; Mahon, M. F.; Richards, S. P.; Whittlesey, M. K. C-C and C-H Bond Activation Reactions in N-Heterocyclic Carbene Complexes of Ruthenium J. Am. Chem. Soc.2002,124,4944-4945. (j) Viciano, M.; Sanau', M.; Peris, E. Ruthenium Janus-Head Complexes with a Triazolediylidene Ligand. Structural Features and Catalytic Applications Organometallics 2007,26,6050-6054. (k) Prades, A.; Viciano, M.; Sanau, M.; Peris, E. Preparation of a Series of "Ru(p-cymene)" Complexes with Different N-Heterocyclic Carbene Ligands for the Catalytic β-Alkylation of Secondary Alcohols and Dimerization of Phenylacetylene Organometallics 2008,27,4254-4259. (1) Gnanamgari, D.; Sauer, E. L. O.; Schley, N. D.; Butler, C.; Incarvito, C. D.; Crabtree, R. H. Iridium and Ruthenium Complexes with Chelating N-Heterocyclic Carbenes: Efficient Catalysts for Transfer Hydrogenation,β-Alkylation of Alcohols, and N-Alkylation of Amines Organometallics 2009,28,321-325. (m) Bappert, E.; Helmchen, G. Synthesis and Application of Complexes of a Novel Chiral Diphenylphosphino-Functionalized N-Heterocyclic Carbene Synlett 2004,1789-1793. (n) Poyatos, M.; Mc-Namara, W.; Incarvito, C.; Clot, E.; Peris, E.; Crabtree, R. H. A Weak Donor, Planar Chelating Bitriazole N-Heterocyclic Carbene Ligand for Ruthenium(II), Palladium(II), and Rhodium Organometallics 2008,27,2128-2136.
[22](a) Meyer, D.; Taige, M. A.; Zeller, A.; Hohlfeld, K.; Ahrens, S.; Strassner, T. Palladium Complexes with Pyrimidine-Functionalized N-Heterocyclic Carbene Ligands:Synthesis, Structure and Catalytic Activity Organometallics 2009,28,2142-2149. (b) Campeau, L.-C.; Thansandote, P.; Fagnou, K. High-Yielding Intramolecular Direct Arylation Reactions with Aryl Chlorides Org. Lett.2005,7,1857-1860.
[23](a) Dastgir, S.; Coleman, K. S.; Cowley, A. R.; Green, M. L. H. A Stable Crystalline Imino-N-Heterocyclic Carbene Ligand and Its Corresponding Palladium(II) and Rhodium(I) ComplexesOrganometallics 2006,25,300-306. (b) Green, M.; McMullin, C. L.; Morton, G. J. P.; Orpen, A. G.; Wass, D. F.; Wingad, R. L Rhodium Complexes of Cyclopropenylidene Carbene Ligands:Synthesis, Structure, and Hydroformylation Catalysis Organometallics 2009,28,1476-1479. (c) Sparta, M.; B(?)rve, K. J.; Jensen, V. R. Activity of Rhodium-Catalyzed Hydroformylation:Added Insight and Predictions from Theory J. Am. Chem. Soc.2007,129,8487-8499.
[24](a) Tudose, A.; Demonceau, A.; Delaude, L. Imidazol(in)ium-2 -carboxylates as N-heterocyclic carbene precursors in ruthenium-arene catalysts for olefin metathesis and cyclopropanation J. Organomet. Chem.2006,691,5356.
[25](a) Sato, Y.; Yoshino, T.; Mori, M. Pd-Catalyzed Allylic Substitution Using Nucleophilic N-Heterocyclic Carbene as a Ligand Org. Lett.2003,5,31-33. (b) Sato, Y.; Yoshino, T.; Mori, M. N-Heterocyclic carbenes as ligands in palladium-catalyzed Tsuji-Trost allylic substitution J. Organomet. Chem.2005,690,5753-5758. For the related allylic amination, see:(c) Visentin, F.; Togni, A. Synthesis and Characterization of Palladium(II) π-Allyl Complexes with Chiral Phosphinocarbene Ligands. Kinetics and Mechanism of Allylic Amination Organometallics 2007,26,3746-3754. (358) Flahaut, A.; Roland, S.; Mangeney, P. Allylic alkylation and amination using mixed (NHC)(phosphine) palladium complexes under biphasic conditions J. Organomet. Chem.2007,692, 5754-5762. (359) Roland, S.; Cotet, W.; Mangeney, P. Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N-Heterocyclic Carbene Ligands Eur. J. Inorg. Chem.2009,1796-1805. (360) Toselli, N.; Martin, D.; Buono, G. Looking for a Synergic Effect between NHCs and Chiral P-Ligands Org. Lett.2008,10,1453-1456.
[26](a) Hanasaka, F.; Fujita, K.-i.; Yamaguchi, R. Cp*Ir Complexes Bearing N-Heterocyclic Carbene Ligands as Effective Catalysts for Oppenauer-Type Oxidation of Alcohols Organometallics 2004,23,1490-1492. (b) Hanasaka, F.; Fujita, K.-i.; Yamaguchi, R. Synthesis of New Cationic Cp*Ir N-Heterocyclic Carbene Complexes and Their High Catalytic Activities in the Oppenauer-Type Oxidation of Primary and Secondary Alcohols Organometallics 2005,24,3422-3433. (c) Hanasaka, F.; Fujita, K.-i.; Yamaguchi, R. Synthesis of New Iridium N-Heterocyclic Carbene Complexes Bearing a Functionalized Cp* Ligand and Their High Catalytic Activities in the Oppenauer-Type Oxidation of Alcohol Organometallics 2006,25,4643-4647. (d) Iwai, Y.; Gligorich, K. M.; Sigman, M. S. Aerobic Alcohol Oxidation Coupled to Palladium-Catalyzed Alkene Hydroarylation with Boronic Esters Angew. Chem., Int. Ed.2008,47,3219-3222. (e) Popp, B. V.; Stahl, S. S. Insertion of Molecular Oxygen into a Palladium-Hydride Bond:Computational Evidence for Two Nearly Isoenergetic Pathways J. Am. Chem. Soc.2007,129,4410-4422. (f) Konnick, M. M.; Stahl, S. S. Reaction of Molecular Oxygen with a PdⅡ-Hydride To Produce a PdⅡ-Hydroperoxide: Experimental Evidence for an HX-Reductive-Elimination Pathway J. Am. Chem. Soc. 2008,130,5753-5762. (g) Popp, B. V.; Wendlandt, J. E.; Landis, C. R.; Stahl, S. S. Reaction of Molecular Oxygen with an NHC-Coordinated Pd0 Complex: Computational Insights and Experimental Implications Angew. Chem., Int. Ed.2007,46, 601-604. (h) Konnick, M. M.; Gandhi, B. A.; Guzei, I. A.; Stahl, S. S. Reaction of Molecular Oxygen with a PdⅡ-Hydride To Produce a PdⅡ-Hydroperoxide:Acid Catalysis and Implications for Pd-Catalyzed Aerobic Oxidation Reactions Angew. Chem., Int. Ed.2006,45,2904-2907.
[27](a) Fournier, P.-A.; Collins, S. K. A Highly Active Chiral Ruthenium-Based Catalyst for Enantioselective Olefin Metathesis. Organometallics 2007,26,2945-2949. (b) Fournier, P.-A.; Savoie, J.; Stenne, B.; Bedard, M.; Grandbois, A.; Collins, S. K. Mechanistically Inspired Catalysts for Enantioselective Desymmetrizations by Olefin Metathesis. Chem. Eur. J.2008,14,8690-8695.
[28](a) Powell, M. T.; Hou, D. R.; Perry, M. C; Cui, X.; Burgess, K. Chiral Imidazolylidine Ligands for Asymmetric Hydrogenation of Aryl Alkenes. J. Am. Chem. Soc.2001,123, 8878-8879. (b) Perry, M. C; Cui, X. H.; Powell, M. T.; Hou, D. R.; Reibenspies, J. H.; Burgess, K. Optically Active Iridium Imidazol-2-ylidene-oxazoline Complexes: Preparation and Use in Asymmetric Hydrogenation of Arylalkenes. J. Am. Chem. Soc. 2003,125,113-123.
[29]Seo, H.; Kim, B. Y.; Lee, J. H.; Park, H.-J.; Son, S. U.; Chung, Y. K. Synthesis of Chiral Ferrocenyl Imidazolium Salts and Their Rhodium(Ⅰ) and Iridium(Ⅰ) Complexes. Organometallics 2003,22,4783-4791.
[30]Lee, S.; Hartwig, J. F. Improved Catalysts for the Palladium-catalyzed Synthesis of Oxindoles by Amide Arylation, Rate Acceleration, Use of Aryl Chloride Substrates and a New Carbene Ligand for Asymmetric Transformations. J. Org. Chem.2001,66, 3402-3415.
[31]Glorius, F.; Altenhoff, G.; Goddard, R.; Lethmann, C. Oxazolines as Chiral Building Blockes for Imidazolium Salts and N-heterocyclic Carbene Ligands. Chem. Commun. 2002,22,2704-2705.
[32]Larsen, A. O.; Leu, W.; Oberhuber, C. N.; Campbell, J. E.; Hoveyda, A. H. Bidentate NHC-Based Chiral Ligands for Efficient Cu-Catalyzed Enantioselective Allylic Alkylations:Structure and Activity of an Air-Stable Chiral Cu Complex. J. Am. Chem. Soc.2004,126,11130-11131.
[33](a) Guillen, F.; Winn, C. L.; Alexakis, A. Enantioselective Copper-catalyzed Conjugated Addition Using Chiral Diaminocarbene Ligands. Tetrahedron:Asymmetry 2001,12, 2083-2086. (b) Pytkowicz, J.; Roland, S.; Manganey, P.; Enantioselective Conjugated Addition of Diethylzinc Using Catalyst:silver(Ⅰ) Diaminocarbenes and Cu(OTf)2. Tetrahedron:Asymmetry 2001,12,2087-2089. (c) Alexakis, A.; Winn, C. L.; Guillen, F.; Pytkowicz, J.; Roland, S.; Mangeney, P. Asymmetric Synthesis with N-heterocyclic Carbenes, Application to The Copper-catalyzed Conjugate Addition. Adv. Synth. Catal. 2003,345,345-348.
[34]Ma, Y.; Song, C.; Ma, C.; Sun, Z.; Chai, Q.; Andrus, M. B. Asymmetric Addition of Aryl Reagents to Enones with Rhodium Dicyclophane Imidazolium Carbene Catalysis Angew. Chem. Int. Ed.2003,42,5871-5874.
[35]Zhang, T.; Shi, M. Chiral Bidentate Bis(N-Heterocyclic Carbene)-Based Palladium Complexes Bearing Carboxylate Ligands:Highly Effective Catalysts for The Enantioselective Conjugate Addition of Arylboronic Acids to Cyclic Enones. Chem. Eur. J.2008,14,3759-3764.
[36]Focken, T.; Rudolph, J.; Bolm, C. Planar Chiral Imidazolium Salts in the Asymmetric Rhodium-Catalyzed 1,2-Addition of Arylboronic Acids to Aldehydes. Synthesis 2005, 429-436.
[37](a) Arao, T.; Kondo, K.; Aoyama, T. Development of an N-heterocyclic Carbene Ligand Based on Concept of Chiral Mimetic.Tetrahedron Lett.2006,47,1417-1420.
[38]Jensen, D. R.; Sigman, M. S. Palladium Catalysts for Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Based on Mechanistic Insight. Org. Lett.2003,5, 63-65.
[39](a) Asano, N.; Nash, R. J.; Molyneux, R. J.; Fleet, G. W. J. Sugar-mimic Glycosidase Inhibitors:Natural Occurrence, Biological Activity and Prospects for Therapeutic Application. Tetrahedron:Asymmetry 2000,11,1645-1680. (b) Watson, P. S.; Jiang, B.; Scott, B. A Diastereoselective Synthesis of 2,4-Disubstituted Piperidines:Scaffolds for Drug Discovery. Org. Lett.2000,2,3679-3681.
[40](a) Mayers, A. I.; Shawe, T. T.; Gottlieb, L. Stereoselective Nucleophilic Addition to Conformationally Constrained Piperidines An Efficient Route to 2-axial-6-equatorial Disubstituted Piperidines. Tetrahedron Lett.1992,33,867. (b) Tawara, J. N.; Lorenz, P.; Stermitz, F. R. J. Piperidine Alkaloids of Spruce (Picea) and Fir (Abies) species. Nat. Prod.1999,62,321-323. (c) Watson, P. S.; Jiang, B.; Scott, B. A Diastereoselective Synthesis of 2,4-Disubstituted Piperidines:Scaffolds for Drug Discovery. Org. Lett. 2000,2,3679-3681. (d) Brooks, C. A.; Comins, D. L. Asymmetric Synthesis of (2S,4R)-4-hydroxypipecolic Acid.Tetrahedron Lett.2000,41,3551-3553. (e) Weintraub, P. M.; Sabol, J. S.; Kane, J. M.; Borcherding, D. R. Recent Advances in The Synthesis of Piperidones and Piperidines. Tetrahedron 2003,59,2953. (f) Buffat, M. G. P. Synthesis of Piperidines.Tetrahedron 2004,60,1701-1709.
[41]See, for example:(a) Pistia-Brueggeman, G.; Hollingsworth, R. I. A Preparation and Scree-ning Strategy for Glycosidase Inhibitors.Tetrahedron 2001,57,8773-8778. (b) Mukhtar, T. A.; Wright, G. D. Streptogramins, Oxazolidinones, and Other Inhibitors of Bacterial Protein Synthesis.Chem. Rev.2005,105,529-542. (c) Aridoss, G.; Balasubtamanian, S.; Parthiban, D.; Kabilan, S.Synthesis and in Vitro Microbiological Evaluation of Imidazo (4,5-b) Pyridinyleth Oxypiperidones. Eur. J. Med. Chem.2006, 41,268-275. (d) Pei, Z.; Li, X.; von Geldern, T. W.; Longenecker, K.; Pireh, D.; Stewart, K. D.; Backes, B. J.; Lai, C.; Libben, T. H.; Ballaron, S. J.; Beno, D. W. A.; Kempf-Grote, A. J.; Sham, H. L. Trevillyan, J. M. Discovery and Structure-Activity Relationships of Piperidinone-and Piperidine-Cons-trained Phenethylamines as Novel, Potent, and Selective Dipeptidyl Peptidase IV Inhibitors. Med. Chem.2007,50, 1983-1987. (e) Jha, A.; Mukherjee, C.; Prasad, A. K.; Parmar, V. S.; De Clercq, E.; Balzarini, J.; Stables, J. P.; Manavathu, E. K.; Shrivastav, A.; Sharma, R. K.; Nienaber, K. H.; Zello, G. A.; Dimmock, J. R. E,E,E-1-(4-Arylamino-4-oxo-2-butenoyl)-3,5-bis--(arylidene)-4-piperidones:A Topographical Study of Some Novel Potent Cytotoxins Bioorg. Med Chem.2007,15,5854-5865. (f) Das, U.; Das, S.; Bandy, B.; Stables, J. P.; Dimmock, J. R. N-Aroyl-3,5-bis(benzylidene)-4-piperidones:A Novel Class of Antimycobacterial Agents. Bioorg. Med. Chem.2008,16,3602-3607.
[42]Champseix, A. A.; Lefur, G. R. Eur. Pat.12,643 Synthesis and Carbon-β NMR of New C-substituted 1,3-dicyanopropanes. Chem. Abstr.1981,94,15175.
[43]Samczuk, S.; Hermans, H. K. F. Ger. Pat.2,642,856; N-Aryl-N(4-piperidinyl) Arylacetam-ides. Chem. Abstr.1977,87,53094.
[44]Ciba-Geigy, Fr. Pat.2,437,405; Basic Substituted Alkylbenzenzenes an Pharma Ceutical Compositions Containing Them. Chem. Abstr.1981,94,83739.
[45]Nalanishi, M.; Shiraki, M.; Kobayakawa, T.; Kobayashi, R. Jpn. Pat.74-03987; Improvement of Baking Processes and Preservation of Bread by Using 1,6-glucosidase.Chem. Abstr.1974,81,12085.
[46]Dimmock, J. R.; Kandepu, N. M.; Nazarali, A. J. Conformational and Quantitative Structureactivity Relationship Study of Cytotoxic 2-arylidenebenzocycloalkanones.1999, 8.
[47]Wang, Z. X. Stereoisomers of N-[1-(2-Hydroxy-2-phenylethyl)-3-methyl-4-piperidyl] N-phenylpropanamide:Synthesis, Stereochemistry, Analgesic Activity, and Opioid Receptor Binding Characteristics. Med. Chem.1995,38,3652-3659.
[48](a)王世玉,王普善.药物与中向体手册北京：化学工业出版社.2004,532-548.(b)陈绘如,肖国民4-哌啶酮类化合物的合成及其在医药领域中的应用.化工中间体,2005,(8)：1-4.
[49]冯亚青,史太昕,周立山等.N-甲基4-哌啶基甲醛的合成研究化学试剂,2001,23(4)：193-194.
[50]Yang, J. C.; Wang, N.; Yang, X. Extracts of Marasmims and Rosaceus L. ES, Piperdinone Derivatives and The Use as Antihypertensive Agents. WO 2005075423, 2005.
[51]For a review of the recent developments in asymmetric routes to substituted piperidines and piperidones, see:(a) Bailey, P. D.; Millwood, P. A.; Smith, P. D. Asymmetric Routes to Substituted Piperidines. Chem. Soc, Chem. Commun.1998,633-640. (b) Laschat, S.; Dickner, T._Stereoselective Synthesis of Piperidines Synthesis 2000,1781-1813. (c) Zhou, P.; Chen, B.-C.; Davis, F. A. Recent Advances in Asymmetric Reactions Using Sulfinimines N-sulfinyl Imines.Tetrahedron 2004,60,8003-8030. (d) Pearson, M. S. M.; Mathe-Allainmat, M.; Fargeas, V.; Lebreton, J._Recent Advances in The Total Synthesis of Piperidine Azasugars. Eur. Org. Chem.2005,11,2159-2191.
[52]Davis, F. A.; Chao, B.; Rao, A. Intramolecular Mannich Reaction in The Asymmetric Synthesis of Polysubstituted Piperidines:Concise Synthesis of the Dendrobate Alkaloid (+)-241D and Its C-4 Epimer. Org. Lett.2001,3,3169-3171.
[53]Ciblat, S.; Besse, P.; Canet, J.-L.; Troin, Y.; Veschambre, H.; Gelas, J.A practical Asymmetric Synthesis of 2,6-cis-disubstituted Piperidines.Tetrahedron:Asymmetry 1999,10,2225-2235.
[54]Ciblat, S.; Calinaud, P.; Canet, J.-L.; Troin, Y. J. A Simple Synthesis of (+) and (-)-alkaloid 241D and C-4 epimers.Chem. Soc., Perkin Trans.2000,1,353-357. (c) Glasson, S. R.; Canet, J.-L.; Troin, Y.A Rapid Stereoselective Access to Highly Substituted Piperidi- -nes.Tetrahedron Lett.2000,41,9797-9802. (d) Carbonnel, S.; Fayet, C.; Gelas, J.; Troi n, Y. Asymmetric Synthesis of C-6 Substituted Pipecolic Acid Derivatives. Tetrahedron Lett.2000,41,8293-8296. (e) Carbonnel, S.; Troin, Y. Heterocycles Stereoselective Syn thesis of C-6 Substituted Pipecolic Acid Derivatives. Formal Synthesis of (+)-Indolizidne 167B and (+)-Indolizidine 209D 2002,57, 1807-1830.
[55]Machetti, F.; Cordero, F. M.; De Sarlo, F.; Brandi, A.Practical Synthesis of Both Enanti omers of Protected 4-oxopipecolic Acid.Tetrahedron 2001,57,4995-4998.
[56]Ma, D.; Sun, H. A Simple and Stereospecfic Route to 2,6-Disubstituted 4-Hydroxypiperidnes. Synthesis of Dendrobate Alkaloid (+)-241D and Formal Synthesis of (-)-Indolizidine.Org. Lett.2000,2,2503-2505.
[57](a)Renault, O.; Guillon, J.; Dallemagne, P.; Rault, S.Efficient Synthesis of 2-aryl-6-methyl-2,3-dihydro-lH-pyridin-4-ones Tetrahedron Lett.2000,41,681-683. (b) Ma, D.; Sun, H. General Route to 2,4,5-Trisubstituted Piperidines from Enantiopure β-Amino Esters. Total Synthesis of Pseudodistomin B Triacetate and Pseudodistomin F. Org. Chem.2000,65,6009-6016.
[58]Weymann, M.; Pfrengle, W.; Schollmeyer, D.; Kunz, H. Enantioselective Syntheses of 2-Alkyl-,2,6-Dialkylpiperidines and Indolizidine Alkaloids Through Diastereoselective Mannich-Michael Reactions. Synthesis 1997,1151-1160.
[59]Kobayashi, S.; Kusakabe, K.; Ishitani, H. Chiral Catalyst Optimization Using Both Solid-Phase and Liquid-Phase Methods in Asymmetric Aza Diels-Alder Reactions. Org. Lett.2000,2,1225-1227.
[60]Kobayashi, S.; Komiyama, S.; Ishitani, H. A Molecular Chameleon:Chromophoric Sensing by a Self-Complexing Molecular Assembly Angew. Chem. Int. Ed.1998,37, 979-981.
[61](a) Sebesta, R.; Pizzuti, M.; Boersma, A. J.; Minnaard, A. J.; Feringa, B. L. Catalytic Enantioselective Conjugate Addition of Dialkylzinc Reagents to N-substituted-2,3-Dehydro 4-piperidones. Chem. Commun.2005,1711-1713. (b) Kranke, B.; Hebrault, D.; Schultz-Kukula, M.; Kunz, H. Arabinosylamine in Asymmetric Syntheses of Chiral Piperidine Alkaloids. Synlett 2004,671-674.
[62]Jack D. Brown, Michael A. Foley, and Daniel L. Comins A Highly Stereocontrolled, Four-Step Synthesis of (±)-Lasubine II. J. Am. Chem. Soc.1988,110,1445-1447.
[63]Syebesta, R.; Pizzuti, M. G.; Boersma, A. J.; Minnaard, A. J.; Feringa, B. L. Catalytic Enantioselective Conjugate Addition of Dialkylzinc Reagents to N-substituted-2,3-dehydro-4-piperidones. Chem. Commun.2005,1711-1713.
[64]Shintani, R.; Tokunaga, N.; Doi, H.; Hayashi, T. A New Entry of Nucleophiles in Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions:Addition of Organozinc Reagents for the Synthesis of 2-Aryl-4-piperidones. J. Am. Chem. Soc.2004,126, 6240-6241.
[65]Jagt, R. B. C.; de Vries, J. G.; Feringa, B. L.; Minnaard, A. Enantioselective Synthesis of 2-Aryl-4-piperidones via Rhodium/Phosphoramidite-Catalyzed Conjugate Addition of Arylboroxines. Org. Lett.2005,7,2433-2435.
[66]Gini, F.; Hessen, B.; Feringa, B. L.; Minnaard, A. Enantioselective Palladium-catalysed Conjugate Addition of Arylsiloxanes. Chem. Commun.2007,710-712.
[67]T. Chen, J.-J. Jiang, Q. Xu, M. Shi, Axially Chiral NHC-Pd(II) Complexes in the Oxidative Kinetic Resolution of Secondary Alcohols Using Molecular Oxygen as a Terminal Oxidant. Org. Lett.2007,9,865-868;
[68]Ma, G. N.; Zhang, T.; Shi, M. Letter Catalytic Enantioselective Arylation of N-Tosylarylimines with Arylboronic Acids Using C2-Symmetric Cationic N-Heterocyclic Carbene Pd2+Diaquo Complexes.Org. Lett.2009,11,875-878.
[69](a) Kozikowski, A. P.; Park, P.-U. Synthesis of Streptazolin:Use of the Aza-Ferrier Reaction in Conjunction with the INOC Process to Deliver a Unique but Sensitive Natural Product Org. Chem.1990,55,4668-4682. (b) Comins, D. L.; Chung, G.; Foley, M. A. Regio-and Stereoselective Addition of Nucleophiles to 1-Phenoxycarbonyl-2,3-dihy-dropyridinium Salts. Heterocycles 1994,37,1121-1140.
[70]Nakaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.; Miyaura, N. Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl-and Alkenylboronic Acids to Enones. J. Am. Chem. Soc.1998,120,5579-5580.
[71](a) Denmark S. E; Amishiro N. Palladium-catalyzed conjugate addition of organosiloxanes to alpha,beta-unsaturated carbonyl compounds and nitroalkenes. J. org. chem.2003,68,6997-7003. (b) Nishikata, T.; Yamamoto, Y.; Miyaura, N.1,4-Addition of arylsiloxanes to enones catalyzed by dicationic palladium(II) complexes in aqueous media. Chem. Lett.2003,32,752-753.
[72](a) Yao, S.; Meng, J. C.; Siuzdak, G.; Finn, M. G.; New Catalysts for the Asymmetric Hydrosilylation of Ketones Discovered by Mass Spectrometry Screening J. Org. Chem. 2003,68,2540-2546. (b) Hu, X.; Chen, H.; Dai, H.; Zheng, Z. Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine Tetrahedron Asymmetry 2003, 14,3415-3421. (c) Tao, B.; Fu, G. C. Application of aNew Family of P,N Ligands to the Highly Enantioselective Hydrosilylation of Aryl Alkyl and Dialkyl Ketones Angew. Chem. Int. Ed.2002,41,3892-3894. (d) Nishibayashi, Y.; Segawa, K.; Ohe, K.; Uemura, S. Chiral Oxazolinyl ferrocene-Phosphine Hybrid Ligand for the Asymmetric Hydrosilylation of Ketones Organometallics 1995,14,5486-5487. (e) Coyne, A. G.; Guiry, P. J. Rhodium-catalysed asymmetric hydrosilylation of ketones using HETPHOX ligands Tetrahedron Lett.2007,48,747-750.
[73]H. Nishiyama, K. Itoh in Catalytic Asymmetric Synthesis,2nd ed. (Ed.:I. Ojima), Wiley-VCH, Weinheim,2000, pp.111-144.
[74](a) Comprehensive Handbook on Hydrosilylation (Ed.:B. Marciniec), Pergamon Press, Oxford,1992. (b)Hydrosilylation:A Comprehensive Review on Recent Advances (Ed.: B. Marciniec), Springer, Heidelberg,2009.
[75](a) E.N. Jacobsen, A. Pfaltz, H. Yamamoto, Comprehensive Asymmetric Catalysis, vol. 1, Springer, Berlin,1999.
[76](a) Lappert, M. F. In Transition Metal Chemistry, Eds:Mηller, A.; Diemann, E., Verlag Chemie, Weinheim,1981, p.287.
[77]Herrmann, W. A.; Baskakov, D.; Herdtweck, E.; Hoffmann, S. D.; Bunlaksananusorn, T.; Rampf, F.; Rodefeld, L. Chiral N-Heterocyclic Carbene Ligands Derived from 2,2'-Bipiperidine and Partially Reduced Biisoquinoline:Rhodium and Iridium Complexes in Asymmetric Catalysis. Organometallics 2006,25,2449-2459.
[78]Faller, J. W.; Fontaine, P. P. Stereodynamics and Asymmetric Hydrosilylation with Chiral Rhodium Complexes Containing a Monodentate N-Heterocyclic Carbene. Organometallics 2006,25,5887-5893.
[79]Enders, D.; Gielen, H.; Breuer, K. Catalytic Asymmetric Hydrosilylation with (triazolinylidene)Rhodium Complexes Containing an Axis of Chirality. Tetrahedron: Asymmetry 1997,8,3571-3574.
[80](a) Gade, L. H.; Cesar, V.; Bellemin-Laponnaz, S. A Modular Assembly of Chiral Oxazolinylcarbene-Rhodium Complexes:Efficient Phosphane-Free Catalysts for the Asymmetric Hydrosilylation of Dialkyl Ketones. Angew. Chem. Int. Ed.2004,43, 1014-1017. (b) Cesar, V.; Bellemin-Laponnaz, S.; Wadepohl, H.; Gade, L. H. Designing theSearch Pathwayin the Development of a New Class of Highly Efficient Stereoselective Hydrosilylation Catalysts. Chem. Eur.J.2005,11,2862-2873.
[81]Yuan, Y.; Raabe, G.; Bolm, C. Novel Rhodium Complexes with Ferrocene-based N-heterocylic Carbenes:Synthesis, Structure and Catalysis. J. Organomet. Chem.2005, 690,5747.
[82]Ros, A.; Alcarazo, M.; Iglesias-Siguenza, J.; Diez, E.; Alvarez, E.; Fernandez, R.; Lassaletta, J. M. Stereoselective Synthesis of Rhodium(I) 4-(Dialkylamino) Triazol-5-ylidene Complexes. Organometallics 2008,27,4555
[83]Chianese, A. R.; Crabtree, R. H. Axially Chiral Bidentate N-Heterocyclic Carbene Ligands Derived from BIN AM:Rhodium and Iridium Complexes in Asymmetric Ketone Hydrosilylation. Organometallics 2005,24,4432-4436.
[84]Song, C.; Ma, C.; Ma, Y.; Feng, W.; Ma, S.; Chai, Q.; Andrus, M. B. Bis-paracyclophane N-heterocyclic Carbene-Ruthenium Catalyzed Asymmetric Ketone Hydrosilylation. Tetrahedron Lett.2005,46,3241-3244.
[85](a) Mori, K. Synthesis of Optically Active Pheromones.Tetrahedron 1989,45,3233. (b) Girard, A.; Greck, C.; Ferroud, D.; Genet, J. P. Syntheses of the Syn and Anti a-amino-β-hydroxy Acids of Vancomycin:(2S,3R) and (2R,3R) P-chloro-3-hydroxytyrosines.Tetrahedron Lett.1996,37,7967. (c) Ali, I. S.; Sudalai, A. Pd-Catalyzed Kinetic Resolution of Benzylic Alcohols:a Practical Synthesis of (R)-tomoxetine and (S)-fluoxetine hydrochlorides.Tetrahedron Lett.2002,43,5435. (d) Wirth, D. D.; Miller, M. S.; Boini, S. K.; Koenig, T. M. Identification and Comparison of Impurities in Fluoxetine Hydrochloride Synthesized by Seven Different Routes. Org. Process Res. Dev.2000,4,513. (e) Hodgetts, K. Approaches to 2-substituted chroman-4-ones:Synthesis of (-)-pinostrobin. J. Tetrahedron Lett.2001,42,3763.
[86](a) Tang, W.; Zhang, X. New Chiral Phosphorus Ligands for Enantioselective Hydrogenation.Chem. Rev.2003,103,3029. (b) McCarthy, M.; Guiry, P. Axially Chiral Bidentate Ligands in Asymmetric Catalysis. Tetrahedron 2001,57,3809. (c) Catalytic Asymmetric Synthesis; Ojima, I. Ed.; Wiley-VCH:Weinheim, Germany,2000. (d) Comprehensive Asymmetric Catalysis; Jacobsen, E. N.; Pfalts, A.; Yamamoto, H. Eds.; Springer:Berlin, Germany,1999.
[87](a) Davies, H. G.; Green, R. H.; Kelly, D. R.; Roberts, S.. In Biotransformations in Preparative Organic Chemistry. The Use of Isolated Enzymes and Whole Cell Systems in Synthesis; Academic Press:London,1989 (Chapter 3). (b) Rodriguez, S.; Kayser, M. M.; Stewart, J. D. Highly Stereoselective Reagents for β-Keto Ester Reductions by Genetic Engineering of Baker's Yeast J. Am. Chem. Soc.2001,123,1547-1555. (c) Buque, E. M.; Chin-Joe, I.; Straathof, A. J. J.; Jongejan, J. A.; Heijnen, J. Immobilization Affects the Rate and Enantioselectivity of 3-oxo Ester Reduction by Baker's Yeast. J. Enzyme Microb. Technol.2002,31,656.
[88](a) Duthaler, R.O.; Herold, P.; Lottenbach, W.; Oertle, K.; Riediker, M. Enantioselective Aldol Reaction of Tert-Butyl Acetate Using Titanium-Carbohydrate Complexes Angew. Chem. Int. Ed. Engl.1989,28,495. (b) Mioskowski, C.; Solladie, G. Syntheses Asymetriques De β-hydroxyacides Par condensation d'anions Enolates d'esters a-sulfinyle Chiraux Sur des Composes Carbonyles.Tetrahedron 1979,36,227. (c) Meyers, A. I.; Knaus, G. Synthesis via oxazolines. VI. An asymmetric Synthesis of P-hydroxy and P-methoxy Alkanoic acids.Tetrahedron Lett.1974,15,1333.
[89]Ocampo R, Dolbier W R. The Reformatsky reaction in organic synthesis Recent advances. Tetrahedron 2004,60,9325-9374
[90](a) Azerad, R.; Buisson, D. In Microbial Reagents in Organic Synthesis; Servi, S., Ed.; Kluwer Academic Publishers:Dordecht, The Netherlands,1992; pp 421. (b) Nakamura, K.; Fuji, M.; Ida, Y. Stereoinversion of Arylethanols by Geotrichum Candidum. Tetrahedron:Asymmetry 2001,12,3147. (c) Padhi, S. K.; Chadha, A. Deracemisation of Aromatic β-Hydroxy Esters Using Immobilised Whole Cells of Candida Parapsilosis ATCC 7330 and Determination of Absolute Configuration by 1H NMR.Tetrahedron: Asymmetry 2005,16,2790.
[91]Xu, C.; Yuan,C. Candida Rugosa Lipase-catalyzed Kinetic Resolution of β-hydroxy-β-arylpropi Onates and δ-hydroxy-δ-aryl-β-oxo-pentanoates. Tetrahedron 2005,61,2169.
[92]Cesar, V.; Bellemin-Laponnaz, S.; Wadepohl, H.; Gade, L. H. Designing the "Search Pathway" in the Development of a New Class of Highly Efficient Stereoselective Hydrosilylation Catalysts. Chem. Eur.2005,11,2862.
[93]Tsuji, J. Palladium reagents and catalysts[C]. New York:J. Wiley,2004.
[94](a) Zhou, J.; Fu, G. C. Palladium-Catalyzed Negishi Cross-Coupling Reactions of Unactivated Alkyl Iodides, Bromides, Chlorides, and Tosylates J. Am. Chem. Soc.2003, 125,12527-12530. (b) Lee, H.-M.; Nolan, S. P. Efficient Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyl-or Vinyltrimethoxysilane Mediated by a Palladium/Imidazolium Chloride System Org. Lett.2000,2,2053-2055.
[95]Herrmann, W. A. N-Heterocyclic carbenes:A new concept in organometallic catalysis. Angew. Chem. Int. Ed.2002,41,1290-1309.
[96]Miyaura, N.; Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds Chem. Rev.1995,95,2457-2483.
[97](a) Heck, R. F. Palladium Reagents in Organic Syntheses; Academic Press:New York, 1985. (b) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. In Principles and Applications of Organotransition Metal Chemistry; University Science:Mill Valley, CA, 1987. (c) Diederich, F., Stang, P. J. Metal-Catalyzed Cross-Coupling Reactions; Wiley-VCH:Weinheim,1998.
[98]Herrmann, W. A.; Reisinger, C. P.; Spiegler, M. Chelating N-heterocyclic carbene ligands in palladium-catalyzed Heck-type reactions. J. Organomet. Chem.1998,557,93-96.
[99](a) Zhang, C; Huang, J.; Trudell, M. L.; Nolan, S. P. Palladium-imidazol-2-ylidene complexes as catalysts for facile and efficient Suzuki cross-coupling reactions of aryl chlorides with arylboronic acids. J. Org. Chem.1999,64,3804-3805. (b) Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.; Trudell, M. L.; Nolan, S. P. Suzuki-Miyaura cross-coupling reactions mediated by palladium/imidazolium salt systems. Organometallics 2002,21,2866-2873.
[100](a) Navarro, O.; Marion, N.; Mei, J.; Nolan, S. P. Rapid room temperature Buchwald-Hartwig and Suzuki-Miyaura couplings of heteroaromatic compounds employing low catalyst loadings. Chem. Eur. J.2006,12,5142-5148. (b) Singh, R.; Viciu, M. S.; Kramareva, N.; Navarro, O.; Nolan, S. P. Simple (Imidazol-2-ylidene)-Pd-acetate complexes as effective precatalysts for sterically hindered Suzuki-Miyaura couplings. Org. Lett.2005,7,1829-1832.
[101](a) Cabri, W.; Candiani, I. Recent Developments and New Perspectives in the Heck Reaction Acc.Chem. Res.1995,28,2-7. (b) Dounay, A. B.; Overman, L. E. The Asymmetric Intramolecular Heck Reaction in Natural Product Total Synthesis Chem. Rev.2003,103,2945-2964.
[102](a) Shibasaki, M.; Boden, C. O. J.; Kojima, A. The asymmetric Heck reaction Tetrahedron 1997,53,7371-7395. (b) Beletskaya, I. P.; Cheprakov, A. V. The Heck Reaction as a Sharpening Stone of Palladium Catalysis Chem. Rev.2000,100, 3009-3066. (c) Whitcombe, N. J.; Hii, K. K.; Gibson, S. E. Advances in the Heck chemistry of aryl bromides and chlorides Tetrahedron 2001,57,7449-7476. (d) Littke, A. F.; Fu, G. C. Palladium-Catalyzed Coupling Reactions of Aryl Chlorides Angew. Chem., Int. Ed.2002,41,4176-4211. (e) Alonso, F.; Beletskaya, I. P.; Yus, M. Non-conventional methodologies for transition-metal catalysed carbon-carbon coupling: a criticalo verview.Part 1:The Heck reaction Tetrahedron 2005,61,11771-11835.
[103](a) Ikeda, Y.; Nakamura, T.; Yorimitsu, H.; Oshima, K Cobalt-Catalyzed Heck-Type Reaction of Alkyl Halides with Styrenes. J. Am. Chem. Soc.2002,124,6514-6515. (b) Fujioka, T.; Nakamura, T.; Yorimitsu, H.; Oshima, K. Cobalt-Catalyzed Intramolecular Heck-Type Reaction of 6-Halo-1-hexene Derivatives Org. Lett.2002,4,2257-2259.
[104](a) Iyer, S.; Ramesh, C.; Sarkar, A.; Wadgaonkar, P. P. The Vinylation of Aryl and Vinyl Halides Catalyzed by Copper Salts Tetrahedron Lett.1997,38,8113-8116.
[105](a) Boldrini, G. P.; Savola, D.; Tagllavini, E.; Trombini, C.; Umanironchi, A. Nickel-catalyzed coupling of activated alkenes with organic halides J. Organomet. Chem. 1986,301,62-64. (b) Lebedev, S. A.; Lopatina, V. S.; Petrov, E. S.; Beletskaya, I. P. Condensation of organic bromides with vinyl compounds catalysed by nickel complexes in the presence of zinc J. Organomet. Chem.1988,344,253-259. (c) Kong, K.-C.; Cheng, C.-H. Synthesis of spiro dienones from internal acetylene and cyclic 3-iodo enones in the presence of nickel bromide and zinc powder Organometallics 1992,11, 1972. (d) Sustmann, S.; Hopp, P.; Holl, P. Reactions of organic halides with olefins under Nio-catalysis. Formal addition of hydrocarbons to CC-double bonds Tetrahedron Lett.1989,30,689.
[106]Eckhardt, M.; Fu, G. C. The first applications of carbene ligands in cross-couplings of alkyl electrophiles:Sonogashira reactions of unactivated alkyl bromides and iodides. J. Am. Chem. Soc.2003,125,13642-13643.