天然产物（+）-Conagenin和（+）-Furanomycin的全合成及铜（Ⅰ）催化的串联反应研究
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摘要
本论文主要讨论了天然产物(+)-Conagenin和(+)-Furanomycin的不对称合成及铜(Ⅰ)催化的2-亚甲基吡咯环及2-亚甲基二氢呋喃环的合成。
第一章天然产物(+)-Conagenin的不对称合成
介绍了(+)-Conagenin及其类似物全合成研究进展。结合本实验室在合成α-氨基酸方面的经验，我们将手性摸板三环亚胺内酯应用到天然产物(+)-Conagenin的不对称全合成之中，提出了一条简便可行，目前路线最短的方案，从三环亚胺内酯出发经4步高选择性，高产率的合成了所需的(S)-甲基-丝氨酸甲酯。
第二章天然产物(+)-Furanomycin的不对称合成
介绍了(+)-Furanomycin及其类似物全合成研究进展。完成了天然产物(+)-Conagenin及其类似物全合成之后，我们尝试合成另一个天然产物小分子(+)-Furanomycin，利用我们的手性摸板三环亚胺内酯与醛的反应规律，设计了一条简便合理的路线。目前以Z／E比值为44∶1得到了所需顺式α，β-不饱和醛，并且高选择性的得到aldol产物，为完成(+)-Furanomycin奠定了基础。
第三章铜(Ⅰ)催化的2-亚甲基吡咯环衍生物的合成。
介绍了吡咯环衍生物合成研究进展，并对该类反应进行了扩展研究。我们利用碱和铜(Ⅰ)共同催化的曼尼希、氢氨化串联反应，发展了一条有效合成2-亚甲基吡咯环的方法。此外，我们对反应历程进行了更深入的研究，提出了合理的机理。
第四章铜(Ⅰ)催化的2-亚甲基二氢呋喃环衍生物的合成。
在本组利用碱和铜(Ⅰ)共同催化的曼尼希、氢氨化串联反应合成2-亚甲基吡咯环的基础上，我们又成功的完成了2-亚甲基二氢呋喃环的合成。由于该方法是在室温下通过分子内炔基烷氧化反应而完成的，因此该反应的区域选择性非常好，反应速率很快，而且催化剂用量小。
The thesis aims at the studies on Asymmetric synthesis of (+)-Conagenin and(+)-Furanomycin and Copper(I)-catalyzed cascade reactions for the direct synthesis of2-methylenepyrrolidines
PartⅠAsymmetric synthesis of natural product (+)-Conagenin
Introduced the progress in the total synthesis of natural product (+)-Conagenin andisomers. Taking most advantage of successful methods of synthesizing or-amino acids,we applied tricyclic iminolactones into the total synthesis of natural product(+)-Conagenin and designed a short practicable route that the methyl (S)-methylserinewas synthesized starting from them for 4 steps with high diastereoslective and highyield.
PartⅡAsymmetric synthesis of natural product (+)-Furanomycin
Introduced the progress in the total synthesis of natural product (+)-Conagenin andisomers. After finishing the total synthesis of natural product (+)-Conagenin, we triedto synthesis the other natural product (+)-Furanomycin. A reasonable route wasdesigned to finish it by exploiting the rule of tricyclic iminolactones and aromatic oraliphatie aldehyde. Now, we have prepared theα,β-unsaturated aldehyde(Z/E=44:1)and the aldol product in high selectivity.
PartⅢCopper(I)-catalyzed cascade reactions for the direct synthesis of2-methylenepyrrolidines
Introduced the progress in the synthesis of pyrrolidine derivatives and extended tostudy on the reaction. We have developed an efficient method for the synthesis of2-methylenepyrrolidines through base and copper(I)-catalyzed Mannich、hydroamination cascade reaction. What's more, a rational mechanism has beenproposed by deeply studies the reaction process.
PartⅣCopper(I)-catalyzed reactions for the direct synthesis of 2-methylene-dihydrofurans
Taking most advantage of successful methods for the synthesis of2-methylenepyrrolidines through base and copper(I)-catalyzed Mannich、hydroamination cascade reaction, we have also developed an efficient approach forthe synthesis of 2-methylene-dihydrofurans. The reaction is believed to have a goodregioselectivity and rate with small amount of catalyst.
第一章天然产物(+)-Conagenin的不对称合成
介绍了(+)-Conagenin及其类似物全合成研究进展。结合本实验室在合成α-氨基酸方面的经验，我们将手性摸板三环亚胺内酯应用到天然产物(+)-Conagenin的不对称全合成之中，提出了一条简便可行，目前路线最短的方案，从三环亚胺内酯出发经4步高选择性，高产率的合成了所需的(S)-甲基-丝氨酸甲酯。
第二章天然产物(+)-Furanomycin的不对称合成
介绍了(+)-Furanomycin及其类似物全合成研究进展。完成了天然产物(+)-Conagenin及其类似物全合成之后，我们尝试合成另一个天然产物小分子(+)-Furanomycin，利用我们的手性摸板三环亚胺内酯与醛的反应规律，设计了一条简便合理的路线。目前以Z／E比值为44∶1得到了所需顺式α，β-不饱和醛，并且高选择性的得到aldol产物，为完成(+)-Furanomycin奠定了基础。
第三章铜(Ⅰ)催化的2-亚甲基吡咯环衍生物的合成。
介绍了吡咯环衍生物合成研究进展，并对该类反应进行了扩展研究。我们利用碱和铜(Ⅰ)共同催化的曼尼希、氢氨化串联反应，发展了一条有效合成2-亚甲基吡咯环的方法。此外，我们对反应历程进行了更深入的研究，提出了合理的机理。
第四章铜(Ⅰ)催化的2-亚甲基二氢呋喃环衍生物的合成。
在本组利用碱和铜(Ⅰ)共同催化的曼尼希、氢氨化串联反应合成2-亚甲基吡咯环的基础上，我们又成功的完成了2-亚甲基二氢呋喃环的合成。由于该方法是在室温下通过分子内炔基烷氧化反应而完成的，因此该反应的区域选择性非常好，反应速率很快，而且催化剂用量小。
The thesis aims at the studies on Asymmetric synthesis of (+)-Conagenin and(+)-Furanomycin and Copper(I)-catalyzed cascade reactions for the direct synthesis of2-methylenepyrrolidines
PartⅠAsymmetric synthesis of natural product (+)-Conagenin
Introduced the progress in the total synthesis of natural product (+)-Conagenin andisomers. Taking most advantage of successful methods of synthesizing or-amino acids,we applied tricyclic iminolactones into the total synthesis of natural product(+)-Conagenin and designed a short practicable route that the methyl (S)-methylserinewas synthesized starting from them for 4 steps with high diastereoslective and highyield.
PartⅡAsymmetric synthesis of natural product (+)-Furanomycin
Introduced the progress in the total synthesis of natural product (+)-Conagenin andisomers. After finishing the total synthesis of natural product (+)-Conagenin, we triedto synthesis the other natural product (+)-Furanomycin. A reasonable route wasdesigned to finish it by exploiting the rule of tricyclic iminolactones and aromatic oraliphatie aldehyde. Now, we have prepared theα,β-unsaturated aldehyde(Z/E=44:1)and the aldol product in high selectivity.
PartⅢCopper(I)-catalyzed cascade reactions for the direct synthesis of2-methylenepyrrolidines
Introduced the progress in the synthesis of pyrrolidine derivatives and extended tostudy on the reaction. We have developed an efficient method for the synthesis of2-methylenepyrrolidines through base and copper(I)-catalyzed Mannich、hydroamination cascade reaction. What's more, a rational mechanism has beenproposed by deeply studies the reaction process.
PartⅣCopper(I)-catalyzed reactions for the direct synthesis of 2-methylene-dihydrofurans
Taking most advantage of successful methods for the synthesis of2-methylenepyrrolidines through base and copper(I)-catalyzed Mannich、hydroamination cascade reaction, we have also developed an efficient approach forthe synthesis of 2-methylene-dihydrofurans. The reaction is believed to have a goodregioselectivity and rate with small amount of catalyst.
引文
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(b) Anionic Pd(0) and Pd(Ⅱ) Intermediates in Palladium-Catalyzed Heck and Cross-Coupling Reactions. Amatore, C.; Jutand, A. Acc. Chem. Res. 2000, 33, 314-321.
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(f) Special Issue-"30 Years of the Cross-coupling Reaction". J. Organomet. Chem. 2002, 653, 1-303.
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(b) Minami, T.; Ozawa, F. Kagaku (Kyoto) 1997, 52, 66; Chem. Abstr. 1997, 126, 334967.
(c) Palladium catalysed pronucleophile addition to unactivated carbon-carbon multiple bonds; Yamamoto, Y.; Radhakrishnan, U. Chem. Soc. Rev. 1999, 28, 199-207.
(d) Catalytic Heterofunctionalization; Togni, A., Gr(u|¨) tzmacher, H., Eds.; Wiley-VCH: Weinheim, 2001.
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(b) Brunet, J. J.; Neibecker, D.; Niedercorn, F. J. Mol. Catal. 1989, 49, 235.
(c) In Applied Homogeneous Catalysis with Organometallic Compounds; Taube, R. Cornils, B., Herrmann, W. A., Eds.; VCH: Weinheim, 1996; Vol. 1, pp 507-520.
(d) In Transition Metals for Organic Synthesis; M(u|¨) ller, T. E.; Belier, M. Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, 1998; Vol. 2, pp 316-330.
(e) Metal-Initiated Amination of Alkenes and Alkynes; Mu(a|¨)ller, T. E.; Belier, M. Chem. Rev. 1998, 98, 675-704.
(f) Katalytische Hydroaminierung von Alkenen und Alkinen; Haak, E.; Doye, S. Chem. unserer Zeit 1999, 33, 297-303.
(g) Reference le, Chapter 4.
(h) Modern Amination Methods; Ricci, A. Wiley-VCH: Weinheim, 2000.
(i) Recent Developments in Transition Metal Catalyzed Intermolecular Hydroamination Reactions - A Breakthrough; Nobis, M.; Driessen-H(o|¨) lscher, B. Angew. Chem., Int. Ed. 2001, 40, 3983-3985.
(j) Tropos or Atropos? That is the Question!; Beller, M.; Breindl, C.; Eichberger, M.; Hartung, C. G.; Seayad, J.; Thiel, O. R.; Tillack, A.; Trauthwein, H. Synlett 2002, 1561-1578.
(k) In Encyclopedia of Catalysis; M(u|¨) ller, T. E. Horva' th, I. T., Ed.; Wiley: New York, 2002. We are very grateful to Prof. T. E. M(u|¨) ller for providing us a copy of the manuscript.
(l) In Handbook of Organopalladium Chemistry for Organic Synthesis; Hosokawa, T. Negishi, E., Ed.; Wiley: Hoboken, 2002; Vol.2, pp 2221-2225.
(m) In Handbook of Organopalladium Chemistry for Organic Synthesis, Cacchi, S.; Marinelli, F. Negishi, E., Ed.; Wiley: Hoboken, 2002; Vol. 2, pp 2227-2244.
5. (a)Generation, alkyne cycloaddition, arene carbon-hydrogen activation, nitrogen-hydrogen activation and dative ligand trapping reactions of the first monomeric imidozirconocene (Cp2Zr:NR) complexes; Walsh, P. J.; Hollander, F. J.; Bergman, R. G. J. Am. Chem. Soc. 1988, 110, 8729-8731.
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(d) Variable regiochemistry in the stoichiometric and catalytic hydroamination of alkynes by imidozirconium complexes caused by an unusual dependence of the rate law on alkyne structure and temperature; Baranger, A. M.; Walsh, P. J.; Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 2753-2763.
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8. Scope of the Intramolecular Imidotitanium-Alkyne[2 + 2]Cycloaddition-Azatita-netine Acylation Sequence. An Efficient Procedure for the Synthesis of 2-(2-Keto-1-alkylidene)tetrahydropyrroles and Related Compounds; Fairfax, D.; Stein, M.; Livinghouse, T.; Jensen, M. Organometallics 1997, 16, 1523-1525.
9. (a) Synthetic applications of Group Ⅳ metal-imido complex - alkyne[2+2]cycloadditions. A concise total synthesis of (.+-.)-monomorine; McGrane, P.L.; Livinghouse, T. J. Org. Chem. 1992, 57, 1323-1324.
(b) Synthetic applications of imidotitanium-alkyne[2+2]cycloadditions. A concise, stereocontrolled total synthesis of the antifungal agent (+)-preussin; McGrane, P. L.; Livinghouse, T. J. Am. Chem. Soc. 1993, 115, 11485-11489.
10. (a) The Cp_2TiMe_2-catalyzed intramolecular hydroamination/cyclization of aminoalkynes ; Bytschkov, I.; Doye, S. Tetrahedron Lett. 2002, 43, 3715-3718.
(b) Ruthenium-catalyzed intramolecular hydroamination of aminoalkynes; See, for instance: Kondo, T.; Okada, T.; Suzuki, T.; Mitsudo, T.-a. J. Organomet. Chem. 2001, 622, 149-154 and references therein.
11. A Three-Component Coupling Process Based on Vicarious Nucleophilic Substitution (VNS_(AR))-Alkylation Reactions: An Approach to Indoprofen and Derivatives; Haak, E.; Bytschkov, I.; Doye, S. Eur. J. Org. Chem. 2002, 67, 457-464.
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13. (a) For a thematic issue on lanthanide chemistry, see: Kagan, H. B., Ed. Frontiers in Lanthanide Chemistry. Chem Rev. 2002, 102, 1805-1806
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14. (a) Organolanthanide-Catalyzed Carbon-Heteroatom Bond Formation. Observations on the Facile, Regiospecific Cyclization of Aminoalkynes; Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439-440.
(b) In Energetics of Organometallic Species; Giardello, M. A.; King, W. A.; Nolan, S. P.; Porchia, M.; Sishta, C.; Marks, T. J. Martino Simoes, J. A., Ed.; Kluwer: Amsterdam, 1992; pp 35-54.
15. (a) Coupled Organolanthanide-Catalyzed C-N/C-C Bond Formation Processes. Efficient Regiospecific Assembly of Pyrrolizidine and Indolizidine Skeletons in a Single Catalytic Reaction; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1996, 118, 707-708.
(b) Organolanthanide-Catalyzed Intra- and Intermolecular Tandem C-N and C-C Bond-Forming Processes of Aminodialkenes, Aminodialkynes, Aminoalkeneynes, and Aminoalkynes. New Regiospecific Approaches to Pyrrolizidine, Indolizidine, Pyrrole, and Pyrazine Skeletons; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1757-1771.
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17. (a) Tokunaga, M.; Wakatsuki, Y. Yuki Gosei Kagaku Kyokaishi 2000, 58, 587; Chem. Abstr. 2000, 133, 73620.
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19. Palladium-catalyzed synthesis of pyrroles; Utimoto, K.; Miwa, H.; Nozaki, H. Tetrahedron Lett. 1981, 22, 4277-4278.
20. Palladium-catalyzed cycloisomerization of (Z)-(2-en-4-ynyl)amines: a new synthesis of substituted pyrroles; Gabriele, B.; Salerno, G.; Fazio, A.; Bossio, M. R. Tetrahedron Lett. 2001, 42, 1339.
21. Palladium-Catalyzed Cyclization Reactions of Acetylene-Containing Amino Acids; Wolf, L. B.; Tjen, K. C. M. F.; ten Brink, H. T.; Blaauw, R. H.; Hiemstra, H.; Schoemaker, H. E.; Rutjes, R. H. Adv. Synth. Catal. 2002, 344
22. (a) A Novel Cu-Assisted Cycloisomerization of Alkynyl Imines: Efficient Synthesis of Pyrroles and Pyrrole-Containing Heterocycles; Kel'in, A. V.; Sromek, A. W.; Gevorgyan, V. J. Am. Chem. Soc. 2001, 123, 2074-2075.
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23. (a) Sequential Ru-Pd Catalysis: A Two-Catalyst One-Pot Protocol for the Synthesis of N- and O-Heterocycles; B. M. Trost, M. R. Machacek, and B. D. Faulk, J. Am. Chem. Soc. 2006, 128, 6745-6754;
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24. (a) Ruthenium-Catalyzed Cycloisomerizations of Diynols; B. M. Trost, M. T. Rudd, J. Am. Chem. Soc. 2005, 127, 4763-4776;
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25. (a)Tandem oxa-Michael addition-S_N2' substitution of 4-chlorobut-2-yn-1-ol with nitroalkenes: a total allylic 1,3-strain-controlled diastereoselective synthesis of 3-vinylidenetetrahydrofurans; J-P. DulcJre, E. Dumez, Chem. Commun. 1997, 971-972.
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26. (a) Twenty-five years of dimethylsulfoxonium ethylide (corey's reagent); M. Cavicchioli, X. Marat, N. Monteiro, B. Hartmann, G. Balme, Tetrahedron Lett. 2002, 43, 2609-2651.
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27. Integrated Transition Metal Catalysed Reactions: Synthesis of Polysubstituted 4-(Phenoxymethyl)-3-pyrrolines and Their Isomers by One-Pot Coupling of Propargylamines, Vinyl Sulfones (or Nitroalkenes) and Phenols; B. Clique, S. Vassiliou, N. Monteiro, G. Balme, Eur. J. Org. Chem. 2002, 1493-1499.
28. (a) S. Yamazaki, M. Yamamoto, A. Sumi, Tetrahedron 2007, 63, 2320;
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(c) Lewis Acid Promoted Cyclization of Enyne Triesters and Diesters; S. Yamazaki, K. Yamada, S. Yamabe, K. Yamamoto, J. Org. Chem. 2002, 67, 2889-2901;
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29. Zinc- and Indium-Promoted Conjugate Addition-Cyclization Reactions of Ethenetricarboxylates with Propargylamines and Alcohol: Novel Methylenepyrrolidine and Methylenetetrahydrofuran Syntheses; S. Morikawa, S. Yamazaki, Y. Furusaki, N. Amano, K. Zenke, K. Kakiuchi, J. Org. Chem. 2006, 71, 3540-3544.
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31. (a) Synthesis of Pyrrole Derivatives by Palladium-Catalyzed Cyclization ofγ,δ-Unsaturated Ketone O-Pentafluorobenzoyloximes. Tsutsui, H.; Kitamura, M.; Narasaka, K. Bull Chem. Soc. Jpn. 2002, 75, 1451.
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32. Palladium-promoted cyclization reactions of aminoalkenes. Pugin, B.; Venanzi, L. M.J. Organomet. Chem. 1981, 214, 125-133.
33. (a) Formamide as a superior nitrogen nucleophile in palladium(Ⅱ) mediated synthesis of imidazolidines. Van Benthem, R. A. T. M.; Hiemstra, H.; Longarela, G. R.; Speckamp, W. N. Tetrahedron Lett. 1994, 35, 9281-9284.
(b) Urea as the most reactive and versatile nitrogen nucleophile for the palladium(Ⅱ)-catalyzed cyclization of unsaturated amines. Tamaru, Y.; Hojo, M.; Higashimura, H.; Yoshida, Z.-I. J. Am. Chem. Soc. 1988, 110, 3994-4002.
34. Palladium-catalyzed cyclization of .omega.-olefinic tosamides. Synthesis of nonaromatic nitrogen heterocycles. Hegedus, L. S.; McKearin, J. M. J. Am. Chem. Soc. 1982, 104, 2444-2451.
35. (a) Palladium-catalyzed intramolecular 1,2-oxidation of allenes. Jonasson, C.; B(a|¨)ckvall, J.-E. Tetrahedron Lett. 1998, 39, 3601-3604.
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36. Metal Ion-Mediated Heteroatom Cyclisations. Application of Aryl/Alkenyl Palladium(Ⅱ)-Based Electrophilic Triggers. Davies, I. W.; Scopes, D. I. C.; Gallagher, T. Synlett 1993, 85-87.
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4. (a) In Comprehensive Heterocyclic Chemistry Ⅱ; R. Benassi, A. R. Katritzky, C. W. Rees, E. F. V. Scriven, Eds.; Pergamon: Oxford, UK, 1996, Vol. 2, pp 259-295.
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11. (a) The first synthesis of 4-trifluoromethyl-2H-pyrans by palladium-catalyzed cyclization of (E)-3-alkynyl-3-trifluoromethyl allylic alcohols; F.-L. Qing, W.-Z. Gao, Tetrahedron Lett. 2000, 41, 7727-7730.
(b) B. Gabriele, G. Salerno, F. De Pascali, M. Costa, G. P. Chiusoli, An Efficient and General Synthesis of Furan-2-acetic Esters by Palladium-Catalyzed Oxidative Carbonylation of (Z)-2-En-4-yn-1-ols. J. Org. Chem. 1999, 64, 7693-7699.
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12 Pd(Ⅱ) Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalyst: Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes; N. Asao, T. Nogami, K. Takahashi, Y. Yamamoto, J. Am. Chem. Soc. 2002, 124, 764-765.
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(b) Minami, T.; Ozawa, F. Kagaku (Kyoto) 1997, 52, 66; Chem. Abstr. 1997, 126, 334967.
(c) Palladium catalysed pronucleophile addition to unactivated carbon-carbon multiple bonds; Yamamoto, Y.; Radhakrishnan, U. Chem. Soc. Rev. 1999, 28, 199-207.
(d) Catalytic Heterofunctionalization; Togni, A., Gr(u|¨) tzmacher, H., Eds.; Wiley-VCH: Weinheim, 2001.
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(b) Brunet, J. J.; Neibecker, D.; Niedercorn, F. J. Mol. Catal. 1989, 49, 235.
(c) In Applied Homogeneous Catalysis with Organometallic Compounds; Taube, R. Cornils, B., Herrmann, W. A., Eds.; VCH: Weinheim, 1996; Vol. 1, pp 507-520.
(d) In Transition Metals for Organic Synthesis; M(u|¨) ller, T. E.; Belier, M. Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, 1998; Vol. 2, pp 316-330.
(e) Metal-Initiated Amination of Alkenes and Alkynes; Mu(a|¨)ller, T. E.; Belier, M. Chem. Rev. 1998, 98, 675-704.
(f) Katalytische Hydroaminierung von Alkenen und Alkinen; Haak, E.; Doye, S. Chem. unserer Zeit 1999, 33, 297-303.
(g) Reference le, Chapter 4.
(h) Modern Amination Methods; Ricci, A. Wiley-VCH: Weinheim, 2000.
(i) Recent Developments in Transition Metal Catalyzed Intermolecular Hydroamination Reactions - A Breakthrough; Nobis, M.; Driessen-H(o|¨) lscher, B. Angew. Chem., Int. Ed. 2001, 40, 3983-3985.
(j) Tropos or Atropos? That is the Question!; Beller, M.; Breindl, C.; Eichberger, M.; Hartung, C. G.; Seayad, J.; Thiel, O. R.; Tillack, A.; Trauthwein, H. Synlett 2002, 1561-1578.
(k) In Encyclopedia of Catalysis; M(u|¨) ller, T. E. Horva' th, I. T., Ed.; Wiley: New York, 2002. We are very grateful to Prof. T. E. M(u|¨) ller for providing us a copy of the manuscript.
(l) In Handbook of Organopalladium Chemistry for Organic Synthesis; Hosokawa, T. Negishi, E., Ed.; Wiley: Hoboken, 2002; Vol.2, pp 2221-2225.
(m) In Handbook of Organopalladium Chemistry for Organic Synthesis, Cacchi, S.; Marinelli, F. Negishi, E., Ed.; Wiley: Hoboken, 2002; Vol. 2, pp 2227-2244.
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8. Scope of the Intramolecular Imidotitanium-Alkyne[2 + 2]Cycloaddition-Azatita-netine Acylation Sequence. An Efficient Procedure for the Synthesis of 2-(2-Keto-1-alkylidene)tetrahydropyrroles and Related Compounds; Fairfax, D.; Stein, M.; Livinghouse, T.; Jensen, M. Organometallics 1997, 16, 1523-1525.
9. (a) Synthetic applications of Group Ⅳ metal-imido complex - alkyne[2+2]cycloadditions. A concise total synthesis of (.+-.)-monomorine; McGrane, P.L.; Livinghouse, T. J. Org. Chem. 1992, 57, 1323-1324.
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10. (a) The Cp_2TiMe_2-catalyzed intramolecular hydroamination/cyclization of aminoalkynes ; Bytschkov, I.; Doye, S. Tetrahedron Lett. 2002, 43, 3715-3718.
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11. A Three-Component Coupling Process Based on Vicarious Nucleophilic Substitution (VNS_(AR))-Alkylation Reactions: An Approach to Indoprofen and Derivatives; Haak, E.; Bytschkov, I.; Doye, S. Eur. J. Org. Chem. 2002, 67, 457-464.
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14. (a) Organolanthanide-Catalyzed Carbon-Heteroatom Bond Formation. Observations on the Facile, Regiospecific Cyclization of Aminoalkynes; Li, Y.; Fu, P.-F.; Marks, T. J. Organometallics 1994, 13, 439-440.
(b) In Energetics of Organometallic Species; Giardello, M. A.; King, W. A.; Nolan, S. P.; Porchia, M.; Sishta, C.; Marks, T. J. Martino Simoes, J. A., Ed.; Kluwer: Amsterdam, 1992; pp 35-54.
15. (a) Coupled Organolanthanide-Catalyzed C-N/C-C Bond Formation Processes. Efficient Regiospecific Assembly of Pyrrolizidine and Indolizidine Skeletons in a Single Catalytic Reaction; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1996, 118, 707-708.
(b) Organolanthanide-Catalyzed Intra- and Intermolecular Tandem C-N and C-C Bond-Forming Processes of Aminodialkenes, Aminodialkynes, Aminoalkeneynes, and Aminoalkynes. New Regiospecific Approaches to Pyrrolizidine, Indolizidine, Pyrrole, and Pyrazine Skeletons; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1757-1771.
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17. (a) Tokunaga, M.; Wakatsuki, Y. Yuki Gosei Kagaku Kyokaishi 2000, 58, 587; Chem. Abstr. 2000, 133, 73620.
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19. Palladium-catalyzed synthesis of pyrroles; Utimoto, K.; Miwa, H.; Nozaki, H. Tetrahedron Lett. 1981, 22, 4277-4278.
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22. (a) A Novel Cu-Assisted Cycloisomerization of Alkynyl Imines: Efficient Synthesis of Pyrroles and Pyrrole-Containing Heterocycles; Kel'in, A. V.; Sromek, A. W.; Gevorgyan, V. J. Am. Chem. Soc. 2001, 123, 2074-2075.
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23. (a) Sequential Ru-Pd Catalysis: A Two-Catalyst One-Pot Protocol for the Synthesis of N- and O-Heterocycles; B. M. Trost, M. R. Machacek, and B. D. Faulk, J. Am. Chem. Soc. 2006, 128, 6745-6754;
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24. (a) Ruthenium-Catalyzed Cycloisomerizations of Diynols; B. M. Trost, M. T. Rudd, J. Am. Chem. Soc. 2005, 127, 4763-4776;
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25. (a)Tandem oxa-Michael addition-S_N2' substitution of 4-chlorobut-2-yn-1-ol with nitroalkenes: a total allylic 1,3-strain-controlled diastereoselective synthesis of 3-vinylidenetetrahydrofurans; J-P. DulcJre, E. Dumez, Chem. Commun. 1997, 971-972.
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26. (a) Twenty-five years of dimethylsulfoxonium ethylide (corey's reagent); M. Cavicchioli, X. Marat, N. Monteiro, B. Hartmann, G. Balme, Tetrahedron Lett. 2002, 43, 2609-2651.
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27. Integrated Transition Metal Catalysed Reactions: Synthesis of Polysubstituted 4-(Phenoxymethyl)-3-pyrrolines and Their Isomers by One-Pot Coupling of Propargylamines, Vinyl Sulfones (or Nitroalkenes) and Phenols; B. Clique, S. Vassiliou, N. Monteiro, G. Balme, Eur. J. Org. Chem. 2002, 1493-1499.
28. (a) S. Yamazaki, M. Yamamoto, A. Sumi, Tetrahedron 2007, 63, 2320;
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31. (a) Synthesis of Pyrrole Derivatives by Palladium-Catalyzed Cyclization ofγ,δ-Unsaturated Ketone O-Pentafluorobenzoyloximes. Tsutsui, H.; Kitamura, M.; Narasaka, K. Bull Chem. Soc. Jpn. 2002, 75, 1451.
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32. Palladium-promoted cyclization reactions of aminoalkenes. Pugin, B.; Venanzi, L. M.J. Organomet. Chem. 1981, 214, 125-133.
33. (a) Formamide as a superior nitrogen nucleophile in palladium(Ⅱ) mediated synthesis of imidazolidines. Van Benthem, R. A. T. M.; Hiemstra, H.; Longarela, G. R.; Speckamp, W. N. Tetrahedron Lett. 1994, 35, 9281-9284.
(b) Urea as the most reactive and versatile nitrogen nucleophile for the palladium(Ⅱ)-catalyzed cyclization of unsaturated amines. Tamaru, Y.; Hojo, M.; Higashimura, H.; Yoshida, Z.-I. J. Am. Chem. Soc. 1988, 110, 3994-4002.
34. Palladium-catalyzed cyclization of .omega.-olefinic tosamides. Synthesis of nonaromatic nitrogen heterocycles. Hegedus, L. S.; McKearin, J. M. J. Am. Chem. Soc. 1982, 104, 2444-2451.
35. (a) Palladium-catalyzed intramolecular 1,2-oxidation of allenes. Jonasson, C.; B(a|¨)ckvall, J.-E. Tetrahedron Lett. 1998, 39, 3601-3604.
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3. (a) The Logic of Chemical Synthesis; E. J. Corey, X.-M. Cheng, J. Wiley: New York, 1989.
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4. (a) In Comprehensive Heterocyclic Chemistry Ⅱ; R. Benassi, A. R. Katritzky, C. W. Rees, E. F. V. Scriven, Eds.; Pergamon: Oxford, UK, 1996, Vol. 2, pp 259-295.
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11. (a) The first synthesis of 4-trifluoromethyl-2H-pyrans by palladium-catalyzed cyclization of (E)-3-alkynyl-3-trifluoromethyl allylic alcohols; F.-L. Qing, W.-Z. Gao, Tetrahedron Lett. 2000, 41, 7727-7730.
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