摘要
过渡金属催化C-H活化提供了绿色、原子经济的化学合成方法。多种过渡金属(Pd、Ru、Ir等)催化的C-H活化官能化反应得到广泛的研究。近年来,Rh(III)催化C-H活化反应也得到了充分的发展,并为重要活性药物分子合成提供了有效的方法。该论文首先综述了Rh(III)催化C-H活化烯基化、烷基化、氨化等官能化反应以及在杂环合成上的应用。从而得出结论,进一步发展Rh(Ⅲ)催化C-H活化官能化反应及杂环化合物合成的新方法,并实现重要活性药物分子的合成,仍是有机合成化学中一项重要的课题。
1. Rh催化酚酯导向C-H活化氧化Heck反应。我们首次实现酚酯导向的氧化Heck反应。反应可以有效的兼容Br, Cl等基团;多种烯烃底物都可以得到很好的反应。与Pd(Ⅱ)催化的Heck反应相比,反应实现很好的区域选择性控制。反应提供了合成2-烯基取代苯酚衍生物有效方法。
2. Rh催化C-H活化与联烯反应合成共轭烯烃反应。我们实现了Rh催化下C-H活化与联烯化合物反应合成共轭烯烃化合物。反应不仅可以实现烯烃C-H底物的反应,芳基C-H底物也可以得到很好的实现。反应产物可以转化为为其他重要骨架分子。
3.Rh催化C-H活化氰基化反应。首次实现了RRh(Ⅲ)催化下的C-H活化氰基化反应合成芳基腈化合物。反应使用NCTS作为氰基试剂来源,这是一种低毒易得的氰基化试剂。多种导向基都可以实现邻位的C-H活化氰基化反应;反应可以很好的兼容Br、I、酚羟基、环氧等重要的基团;芳香杂环底物也能得到很好的反应效果;反应可以实现复杂分子的C-H氰基化衍生。
4. Rh催化C-H活化合成2-甲基吲哚化合物。我们成功实现了Rh(Ⅲ)催化下,乙酰苯胺衍生物与烯丙醇酯反应得到2-甲基吲哚化合物。反应具有很好的官能团兼容性,Br、I、杂环等重要基团都可以很好的兼容;反应产物可以经过转化得到其他重要结构的化合物;并且我们实现了从简单酰胺原料出发合成两个重要的药物分子。
Transition-metal catalyzed C-H bond activation provides an atom-and step-economical approach for organic synthesis. A variety of transition metals (Pd, Ru, Ir, etc.) catalyzed C-H activation functionalization reaction have been developed. In the past five years, Rh (Ⅲ) catalyzed C-H activation reactions have been fully developed, and provides an effective method for the synthesis of biologically active compounds. This paper first reviews the Rh(III) catalyzed C-H activation functionalization reactions and application in the synthesis of heterocyclic. Notwithstanding these pioneering examples, further development of Rh(III) catalyzed C-H activation reactions reactions is needed in synthetic organic chemistry.
1. Rhodium-Catalyzed C-H Activation/Olefination of Phenol Carbamates. We reported a practical protocol for ortho C-H activation/olefination of phenol carbamates. The reaction tolerates a variety of important functional groups (aryl-Br, aryl-Cl) and many different olefins can be used in this process. This reaction exhibits different reactivity as compared to the Pd-catalyzed processes, this method provide a new approach for the synthesis of ortho-substituted phenols.
2. Rh-catalyzed C-H bond activation with allenes to produce highly unsaturated conjugated olefins. Rh(Ⅲ) catalyzed C-H bond activation with allenes to produce unsaturated conjuncted olefins was reported. The reaction is applicable to both olefin and arene C(Sp2)-H, compatible with varieties of functional groups. The obtained products can be transformed into other important skeletons.
3. Rhodium-catalyzed Directed C-H Cyanation. We report the first example of Rh-catalyzed directed C-H cyanation. N-Cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS), a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this cyanation process and the reaction tolerates a variety of important functional groups (aryl-Br, aryl-I unprotected phenol, epoxide), A number of heteroaromatic nitriles were successfully synthesized by using this method, the reaction may provide a practical tool for rapid derivatization of bioactive compounds.
4. A practical Rh-catalyzed reaction was developed to achieve2-alkyl-substituted indoles synthesis. The reaction can tolerate a variety of synthetically important functional groups (aryl-Br, aryl-I, heterocycle). The indole products can also be transformed into other important skeletons. Two bioactive compounds, i.e. indomethacin and pravadoline were prepared using the new method.
引文
[1](a) Lewis J C, Bergman R G, Ellman J A. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation [J]. Accounts of chemical research,2008,41(8):1013-1025. (b) Chen X, Engle K M, Wang D H, et al. Palladium(Ⅱ)-Catalyzed C-H Activation/C-C Cross-Coupling Reactions:Versatility and Practicality [J]. Angewandte Chemie International Edition, 2009,48(28):5094-5115. (c) Ackermann L, Vicente R, Kapdi A R. Transition-Metal-Catalyzed Direct Arylation of (Hetero) Arenes by C-H Bond Cleavage [J]. Angewandte Chemie International Edition,2009,48(52):9792-9826. (d) Daugulis O, Do H Q, Shabashov D. Palladium-and copper-catalyzed arylation of carbon-hydrogen bonds [J]. Accounts of chemical research,2009, 42(8):1074-1086. (e) Giri R, Shi B F, Engle K M, et al. Transition metal-catalyzed C-H activation reactions:diastereoselectivity and enantioselectivity[J]. Chem. Soc. Rev.,2009,38(11):3242-3272. (f) Mkhalid I A I, Barnard J H, Marder T B, et al. C-H Activation for the construction of C-B bonds[J]. Chemical reviews,2009,110(2):890-931. (g) Lyons T W, Sanford M S. Palladium-catalyzed ligand-directed C-H functionalization reactions [J]. Chemical reviews,2010, 110(2):1147-1169. (h) Sun C L, Li B J, Shi Z J. Pd-catalyzed oxidative coupling with organometallic reagents via C-H activation [J]. Chemical Communications,2010,46(5):677-685. (i) Ackermann L. Metal-catalyzed direct alkylations of (hetero) arenes via C-H bond cleavages with unactivated alkyl halides [J]. Chemical Communications,2010,46(27):4866-4877. (j) Jazzar R, Hitce J, Renaudat A, et al. Functionalization of Organic Molecules by Transition-Metal-Catalyzed C(sp3)-H Activation[J]. Chemistry-A European Journal,2010,16(9):2654-2672. (k) McMurray L, O'Hara F, Gaunt M J. Recent developments in natural product synthesis using metal-catalysed C-H bond functionalisation [J]. Chemical Society Reviews,2011,40(4):1885-1898. (1) Yeung C S, Dong V M. Catalytic Dehydrogenative Cross-Coupling:Forming Carbon-Carbon Bonds by Oxidizing Two Carbon-Hydrogen Bonds[J]. Chemical reviews,2011,111(3):1215-1292. (m) Gutekunst W R, Baran P S. C-H functionalization logic in total synthesis [J]. Chemical Society Reviews,2011,40(4): 1976-1991. (n) Hartwig J F. Regioselectivity of the borylation of alkanes and arenes [J]. Chemical Society Reviews,2011,40(4):1992-2002. (o) Cho S H, Kim J Y, Kwak J, et al. Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation [J]. Chemical Society Reviews,2011,40(10):5068-5083. (p) Engle K M, Mei T S, Wasa M, et al. Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions[J]. Accounts of chemical research,2011,45(6):788-802. (q) Colby D A, Tsai A S, Bergman R G, et al. Rhodium Catalyzed Chelation-Assisted C-H Bond Functionalization Reactions [J]. Accounts of chemical research,2011,45(6):814-825. (r) Wencel-Delord J, Droge T, Liu F, et al. Towards mild metal-catalyzed C-H bond activation [J]. Chemical Society Reviews, 2011,40(9):4740-4761. (s) Kuninobu Y, Takai K. Organic reactions catalyzed by rhenium carbonyl complexes[J]. Chemical reviews,2010,111(3):1938-1953. (t) Liu C, Zhang H, Shi W, et al. Bond formations between two nucleophiles:transition metal catalyzed oxidative cross-coupling reactions [J]. Chemical reviews,2011,111(3):1780-1824. (u) Ackermann L. Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations:mechanism and scope [J]. Chemical reviews,2011,111(3):1315-1345. (v) Colby D A, Bergman R G, Ellman J A. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation [J]. Chemical reviews,2009, 110(2):624-655.
[2](a) Satoh T, Miura M. Oxidative coupling of aromatic substrates with alkynes and alkenes under rhodium catalysis[J]. Chemistry-A European Journal,2010,16(37):11212-11222. (b) Colby D A, Tsai A S, Bergman R G, et al. Rhodium Catalyzed Chelation-Assisted C-H Bond Functionalization Reactions[J]. Accounts of chemical research,2011,45(6):814-825. (c) Patureau, F. W.; Wencel-Delord, J.; Glorius, F. Aldrich. Acta.2012,45,31. (d) Song G, Wang F, Li X. C-C, C-O and C-N bond formation via rhodium (Ⅲ)-catalyzed oxidative C-H activation [J]. Chemical Society Reviews,2012,41(9):3651-3678. (e) Zhu C, Wang R, Falck J R. Amide-Directed Tandem C-C/C-N Bond Formation through C-H Activation[J]. Chemistry-An Asian Journal,2012,7(7):1502-1514.
[3](a) Heck R F. Palladium-catalyzed reactions of organic halides with olefins[J]. Accounts of Chemical Research,1979,12(4):146-151. (b) Beletskaya I P, Cheprakov A V. The Heck reaction as a sharpening stone of palladium catalysis [J]. Chemical Reviews,2000,100(8):3009-3066. (c) Nicolaou K C, Bulger P G, Sarlah D. Metathesis reactions in total synthesis [J]. Angewandte Chemie International Edition,2005,44(29):4490-4527. (d) The Mizoroki-Heck Reaction [M]. Chichester, UK:Wiley,200
[4]Umeda N, Hirano K, Satoh T, et al. Rhodium-Catalyzed Mono-and Divinylation of 1-Phenylpyrazoles and Related Compounds via Regioselective C-H Bond Cleavage [J]. The Journal of organic chemistry,2009,74(18):7094-7099.
[5](a) Mochida S, Hirano K, Satoh T, et al. Rhodium-Catalyzed Regioselective Olefination Directed by a Carboxylic Group[J]. The Journal of organic chemistry,2011,76(9):3024-3033. (b) Mochida S, Hirano K, Satoh T, et al. Synthesis of Stilbene and Distyrylbenzene Derivatives through Rhodium-Catalyzed Ortho-Olefination and Decarboxylation of Benzoic Acids [J]. Organic letters, 2010,12(24):5776-5779.
[6]Patureau F W, Glorius F. Rh Catalyzed Olefination and Vinylation of Unactivated Acetanilides [J]. Journal of the American Chemical Society,2010,132(29):9982-9983.
[7]Patureau F W, Besset T, Glorius F. Rhodium-Catalyzed Oxidative Olefination of C-H Bonds in Acetophenones and Benzamides [J]. Angewandte Chemie International Edition,2011,50(5): 1064-1067.
[8]Zhao P, Niu R, Wang F, et al. Rhodium (Ⅲ)-and Ruthenium (Ⅱ)-Catalyzed Olefination of Isoquinolones [J]. Organic letters,2012,14(16):4166-4169.
[9]Wang Y, Li C, Li Y, et al. Rhodium-Catalyzed C-H Olefination of Aryl Weinreb Amides [J]. Advanced Synthesis & Catalysis,2013,355(9):1724-1728.
[10]Tsai A S, Brasse M, Bergman R G, et al. Rh (Ⅲ)-Catalyzed Oxidative Coupling of Unactivated Alkenes via C-H Activation [J]. Organic letters,2010,13(3):540-542.
[11]Rakshit S, Grohmann C, Besset T, et al. Rh (Ⅲ)-Catalyzed Directed C-H Olefination Using an Oxidizing Directing Group:Mild, Efficient, and Versatile [J]. Journal of the American Chemical Society,2011,133(8):2350-2353.
[12]Park S H, Kim J Y, Chang S. Rhodium-Catalyzed Selective Olefination of Arene Esters via C-H Bond Activation [J]. Organic letters,2011,13(9):2372-2375.
[13]Besset T, Kuhl N, Patureau F W, et al. RhⅢ-Catalyzed Oxidative Olefination of Vinylic C-H Bonds:Efficient and Selective Access to Di-unsaturated a-Amino Acid Derivatives and Other Linear 1,3-Butadienes[J]. Chemistry-A European Journal,2011,17(26):7167-7171.
[14]Boultadakis-Arapinis M, Hopkinson M N, Glorius F. Using Rh (Ⅲ)-Catalyzed C-H Activation as a Tool for the Selective Functionalization of Ketone-Containing Molecules [J]. Organic letters, 2014,16(6),1630-1633.
[15]Wang C, Chen H, Wang Z, et al. Rhodium (Ⅲ)-Catalyzed C-H Activation of Arenes Using a Versatile and Removable Triazene Directing Group [J]. Angewandte Chemie International Edition, 2012,51(29):7242-7245.
[16]Liu B, Fan Y, Gao Y, et al. Rhodium (Ⅲ)-Catalyzed N-Nitroso-Directed C-H Olefination of Arenes. High-Yield, Versatile Coupling under Mild Conditions [J]. Journal of the American Chemical Society,2012,135(1):468-473.
[17]Huang X, Huang J, Du C, et al. N-Oxide as a Traceless Oxidizing Directing Group:Mild Rhodium (Ⅲ)-Catalyzed C-H Olefination for the Synthesis of ortho-Alkenylated Tertiary Anilines[J]. Angewandte Chemie International Edition,2013,52(49):12970-12974.
[18]Nobushige K, Hirano K, Satoh T, et al. Rhodium (Ⅲ)-Catalyzed Ortho-Alkenylation through C-H Bond Cleavage Directed by Sulfoxide Groups [J]. Organic letters,2014,16(4),1188-1191.
[19]Parthasarathy K, Bolm C. Rhodium (Ⅲ)-Catalyzed Selective ortho-Olefinations of N-Acyl and N-Aroyl Sulfoximines by C-H Bond Activation [J]. Chemistry-A European Journal,2014,20(17), 4896-4900.
[20]Zhang X S, Zhu Q L, Zhang Y F, et al. Controllable Mono-/Dialkenylation of Benzyl Thioethers through Rh-Catalyzed Aryl C-H Activation [J]. Chemistry-A European Journal,2013,
19(36):11898-11903.
[21](a) Zhou J, Li B, Hu F, et al. Rhodium (Ⅲ)-Catalyzed Oxidative Olefination of Pyridines and Quinolines:Multigram-Scale Synthesis of Naphthyridinones[J]. Organic letters,2013,15(13): 3460-3463. (b) Wei X, Wang F, Song G, et al. Rhodium (ⅲ)-catalyzed oxidative mono-and di-olefination of isonicotinamides[J]. Organic & biomolecular chemistry,2012,10(29):5521-5524.
[22]Li H, Li Y, Zhang X S, et al. Pyridinyl directed alkenylation with olefins via Rh (Ⅲ)-catalyzed C-C bond cleavage of secondary arylmethanols [J]. Journal of the American Chemical Society,2011, 133(39):15244-15247.
[23]Schipper D J, Hutchinson M, Fagnou K. Rhodium (Ⅲ)-Catalyzed Intermolecular Hydroarylation of Alkynes [J]. Journal of the American Chemical Society,2010,132(20): 6910-6911.
[24]Hu F, Xia Y, Ye F, et al. Rhodium (Ⅲ)-Catalyzed ortho Alkenylation of N-Phenoxyacetamides with N-Tosylhydrazones or Diazoesters through C-H Activation[J]. Angewandte Chemie,2013.
[25]Liu B, Zhou T, Li B, et al. Rhodium (Ⅲ)-Catalyzed Alkenylation Reactions of 8-Methylquinolines with Alkynes by C(sp3)-H Activation[J]. Angewandte Chemie,2014.
[27]Chan W W, Lo S F, Zhou Z, et al. Rh-catalyzed intermolecular carbenoid functionalization of aromatic C-H bonds by α-diazomalonates [J]. Journal of the American Chemical Society,2012, 134(33):13565-13568.
[28]Yu X, Yu S, Xiao J, et al. Rhodium (Ⅲ)-Catalyzed Azacycle-Directed Intermolecular Insertion of Arene C-H Bonds into α-Diazocarbonyl Compounds[J]. The Journal of organic chemistry,2013, 78(11):5444-5452.
[29]Yang L, Correia C A, Li C J. Grignard-Type Arylation of Aldehydes via a Rhodium-Catalyzed C-H Activation under Mild Conditions [J]. Advanced Synthesis & Catalysis,2011,353(8): 1269-1273.
[30](a) Wang H, Schroeder N, Glorius F. Mild Rhodium (Ⅲ)-Catalyzed Direct C-H Allylation of Arenes with Allyl Carbonates [J]. Angewandte Chemie International Edition,2013,52(20): 5386-5389. (b) Feng C, Feng D, Loh T P. Oxidant-Free Rh (Ⅲ)-Catalyzed Direct C-H Olefination of Arenes with Allyl Acetates [J]. Organic letters,2013,15(14):3670-3673.
[31]Shi Z, Boultadakis-Arapinis M, Glorius F. Rh (Ⅲ)-catalyzed dehydrogenative alkylation of (hetero) arenes with allylic alcohols, allowing aldol condensation to indenes [J]. Chemical Communications,2013,49(58):6489-6491.
[32]Huang L, Wang Q, Qi J, et al. Rh (Ⅲ)-catalyzed ortho-oxidative alkylation of unactivated arenes with allylic alcohols [J]. Chem. Sci.,2013,4(6):2665-2669.
[33]Zhang T, Qi Z, Zhang X, et al. RhⅢ-Catalyzed Hydroacylation Reactions between N-Sulfonyl 2-Aminobenzaldehydes and Olefins[J]. Chemistry-A European Journal,2014,20(12):3283-3287.
[34]Zeng R, Fu C, Ma S. Highly selective mild stepwise allylation of N-methoxybenzamides with allenes[J]. Journal of the American Chemical Society,2012,134(23):9597-9600.
[35]Ye B, Cramer N. A Tunable Class of Chiral Cp Ligands for Enantioselective Rhodium (Ⅲ)-Catalyzed C-H Allylations of Benzamides [J]. Journal of the American Chemical Society,2013, 135(2):636-639.
[36]Zeng R, Wu S, Fu C, et al. Room-Temperature Synthesis of Trisubstituted Allenylsilanes via Regioselective C-H Functionalization[J]. Journal of the American Chemical Society,2013,135(49): 18284-18287.
[37](a) Lyons T W, Sanford M S. Palladium-catalyzed ligand-directed C-H functionalization reactions [J]. Chemical reviews,2010,110(2):1147-1169. (b) Ackermann L, Vicente R, Kapdi A R. Transition-Metal-Catalyzed Direct Arylation of (Hetero) Arenes by C-H Bond Cleavage [J]. Angew andte Chemie International Edition,2009,48(52):9792-9826. (c) Alberico D, Scott M E, Lautens M. Aryl-aryl bond formation by transition-metal-catalyzed direct arylation[J]. Chemical reviews,2007, 107(1):174-238.
[38]Wencel-Delord J, Nimphius C, Wang H, et al. Rhodium (Ⅲ) and Hexabromobenzene-A Catalyst System for the Cross-Dehydrogenative Coupling of Simple Arenes and Heterocycles with Arenes Bearing Directing Groups [J]. Angewandte Chemie International Edition,2012,51(52): 13001-13005.
[39]Dong J, Long Z, Song F, et al. Rhodium or Ruthenium-Catalyzed Oxidative C-H/C-H Cross-Coupling:Direct Access to Extended π-Conjugated Systems [J]. Angewandte Chemie,2013, 125(2):608-612
[40]Qin X, Liu H, Qin D, et al. Chelation-assisted Rh (Ⅲ)-catalyzed C2-selective oxidative C-H/C-H cross-coupling of indoles/pyrroles with heteroarenes[J]. Chem. Sci.,2013,4(5): 1964-1969.
[41]Shang Y, Jie X, Zhao H, et al. Rh (Ⅲ)-Catalyzed Amide-Directed Cross-Dehydrogenative Heteroarylation of Pyridines [J]. Organic letters,2014,16(2),416-419.
[42]Reddy V P, Qiu R, Iwasaki T, et al. Rhodium-Catalyzed Intermolecular Oxidative Cross-Coupling of (Hetero) Arenes with Chalcogenophenes[J]. Organic letters,2013,15(6): 1290-1293.
[43](a) Kuhl N, Hopkinson M N, Glorius F. Selective Rhodium (Ⅲ)-Catalyzed Cross-Dehydrogenative Coupling of Furan and Thiophene Derivatives [J]. Angewandte Chemie International Edition,2012,51(33):8230-8234. (b) Zhang X, Wang F, Qi Z, et al. Rhodium (Ⅲ)-Catalyzed Redox-Neutral C-H Arylation via Rearomatization[J]. Organic letters,2014,16(6): 1586-1589.
[44](a) Siemsen P, Livingston R C, Diederich F. Acetylenic coupling:a powerful tool in molecular construction[J]. Angewandte Chemie International Edition,2000,39(15):2632-2657. (b) Negishi E, Anastasia L. Palladium-catalyzed alkynylation [J]. Chemical reviews,2003,103(5):1979-2018. (c) Toyota S. Rotational isomerism involving acetylene carbon[J]. Chemical reviews,2010,110(9): 5398-5424.
[45]Feng C, Loh T P. Rhodium-Catalyzed C-H Alkynylation of Arenes at Room Temperature [J]. Angewandte Chemie International Edition,2014,53(10):2722-2726.
[46]Xie F, Qi Z, Yu S, et al. Rh(Ⅲ)-and Ir(Ⅲ)-Catalyzed CH Alkynylation of Arenes under Chelation Assistance [J]. Journal of the American Chemical Society,2014,136(12),4780-4787.
[47]Collins K D, Lied F, Glorius F. Preparation of conjugated 1,3-enynes by Rh (Ⅲ)-catalysed alkynylation of alkenes via C-H activation [J]. Chemical Communications,2014,50(34): 4459-4461.
[48](a) Paul F, Patt J, Hartwig J F. Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides[J]. Journal of the American Chemical Society,1994,116(13):5969-5970. (b) Evano G, Blanchard N, Toumi M. Copper-mediated coupling reactions and their applications in natural products and designed biomolecules synthesis [J]. Chemical reviews,2008,108(8):3054-3131. (c) Guram A S, Buchwald S L. Palladium-catalyzed aromatic aminations with in situ generated aminostannanes [J]. Journal of the American Chemical Society,1994,116(17):7901-7902. (d) Cho S H, Kim J Y, Kwak J, et al. Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation [J]. Chemical Society Reviews,2011, 40(10):5068-5083.
[49]Ng K H, Zhou Z, Yu W Y. Rhodium (Ⅲ)-catalyzed intermolecular direct amination of aromatic C-H bonds with N-chloroamines [J]. Organic letters,2011,14(1):272-275.
[50](a) Ng K H, Zhou Z, Yu W Y. [Cp*RhCl2]2-catalyzed ortho-C-H bond amination of acetophenone o-methyloximes with primary N-chloroalkylamines:convenient synthesis of N-alkyl-2-acylanilines [J]. Chemical Communications,2013,49(63):7031-7033. (b) Ng F N, Zhou Z, Yu W Y. [RhⅢ(Cp*)]-Catalyzed ortho-Selective Direct C(sp2)-H Bond Amidation/Amination of Benzoic Acids by N-Chlorocarbamates and N-Chloromorpholines. A Versatile Synthesis of Functionalized Anthranilic Acids [J]. Chemistry-A European Journal,2014,20(15):4474-4480.
[51]Grohmann C, Wang H, Glorius F. Rh[Ⅲ]-Catalyzed C-H Amidation Using Aroyloxycarbamates To Give N-Boc Protected Arylamines [J]. Organic letters,2013,15(12): 3014-3017
[52]Yu S, Wan B, Li X. Rhodium (Ⅲ)-Catalyzed C-H Activation and Amidation of Arenes Using N-Arenesulfonated Imides as Amidating Reagents[J]. Organic letters,2013,15(14):3706-3709.
[53]Wu K, Fan Z, Xue Y, et al. Rh (Ⅲ)-Catalyzed Intermolecular C-H Amination of 1-Aryl-1 H-pyrazol-5 (4 H)-ones with Alkylamines[J]. Organic letters,2014,16(1),42-45.
[54](a) Zhou B, Du J, Yang Y, et al. Rhodium-Catalyzed Direct Addition of Aryl C-H Bonds to Nitrosobenzenes at Room Temperature [J]. Organic letters,2013,15(24):6302-6305. (b) Du J, Yang Y, Feng H, et al. Rhodium-Catalyzed Direct Amination of Arenes with Nitrosobenzenes:A New Route to Diarylamines [J]. Chemistry-A European Journal,2014.
[55]Zhou B, Du J, Yang Y, et al. Rh (Ⅲ)-Catalyzed C-H Amidation with N-Hydroxycarbamates:A New Entry to N-Carbamate-Protected Arylamines [J]. Organic letters,2014,16(2),592-595.
[56]Zhao H, Shang Y, Su W. Rhodium (Ⅲ)-Catalyzed Intermolecular N-Chelator-Directed Aromatic C-H Amidation with Amides [J]. Organic letters,2013,15(19):5106-5109.
[57]Kim J Y, Park S H, Ryu J, et al. Rhodium-Catalyzed Intermolecular Amidation of Arenes with Sulfonyl Azides via Chelation-Assisted C-H Bond Activation[J]. Journal of the American Chemical Society,2012,134(22):9110-9113.
[58]Kim H J, Ajitha M J, Lee Y, et al. Hydrogen-Bond-Assisted Controlled CH Functionalization via Adaptive Recognition of a Purine Directing Group[J]. Journal of the American Chemical Society, 2014,136(3),1132-1140.
[59]Ryu J, Shin K, Park S H, et al. Rhodium-Catalyzed Direct C-H Amination of Benzamides with Aryl Azides:A Synthetic Route to Diarylamines [J]. Angewandte Chemie,2012,124(39): 10042-10046.
[60]Shin K, Baek Y, Chang S. Direct C-H Amination of Arenes with Alkyl Azides under Rhodium Catalysis [J]. Angewandte Chemie,2013,125(31):8189-8194.
[61]Wang H, Yu Y, Hong X, et al. Rhodium-Catalyzed Direct ortho C-N Bond Formation of Aromatic Azo Compounds with Azides[J]. The Journal of organic chemistry,2014,79(7), 3279-3288.
[62]Tang R J, Luo C P, Yang L, et al. Rhodium (Ⅲ)-Catalyzed C(sp2)-H Activation and Electrophilic Amidation with N-Fluorobenzenesulfonimide[J]. Advanced Synthesis & Catalysis, 2013,355(5):869-873.
[63]Zhou B, Yang Y, Shi J, et al. Rhodium-Catalyzed Synthesis of Amides from Aldehydes and Azides by Chelation-Assisted C-H Bond Activation [J]. Chemistry-A European Journal,2013, 19(32):10511-10515.
[64]Zhou B, Du J, Yang Y, et al. Rhodium (Ⅲ)-Catalyzed Intermolecular Direct Amidation of Aldehyde C-H Bonds with N-Chloroamines at Room Temperature [J]. Organic letters,2013,15(12): 2934-2937.
[65](a) Lubriks D, Sokolovs I, Suna E. Indirect C-H Azidation of Heterocycles via Copper-Catalyzed Regioselective Fragmentation of Unsymmetrical λ3-Iodanes[J]. Journal of the American Chemical Society,2012,134(37):15436-15442. (b) Tang C, Jiao N. Copper-Catalyzed C-H Azidation of Anilines under Mild Conditions [J]. Journal of the American Chemical Society, 2012,134(46):18924-18927. (c) Xie F, Qi Z, Li X. Rhodium (Ⅲ)-Catalyzed Azidation and Nitration of Arenes by C-H Activation[J]. Angewandte Chemie,2013,125(45):12078-12082.
[66]Schroder N, Wencel-Delord J, Glorius F. High-Yielding, Versatile, and Practical [Rh(III) Cp*]-Catalyzed Ortho Bromination and Iodination of Arenes [J]. Journal of the American Chemical Society,2012,134(20):8298-8301.
[67]Kuhl N, Schroder N, Glorius F. Rh (Ⅲ)-Catalyzed Halogenation of Vinylic C-H Bonds:Rapid and General Access to Z-Halo Acrylamides [J]. Organic letters,2013,15(15):3860-3863.
[68]Yang Y, Hou W, Qin L, et al. Rhodium-Catalyzed Directed Sulfenylation of Arene C-H Bonds[J]. Chemistry-A European Journal,2014,20(2):416-420.
[69]Hong X, Wang H, Qian G, et al. Rhodium-Catalyzed Direct C-H Bond Cyanation of Arenes with Isocyanide[J]. The Journal of organic chemistry,2014.
[70]Hesp K D, Bergman R G, Ellman J A. Expedient Synthesis of N-Acyl Anthranilamides and β-Enamine Amides by the Rh (Ⅲ)-Catalyzed Amidation of Aryl and Vinyl C-H Bonds with Isocyanates[J]. Journal of the American Chemical Society,2011,133(30):11430-11433.
[71](a) Tsai A S, Tauchert M E, Bergman R G, et al. Rhodium (Ⅲ)-Catalyzed Arylation of Boc-Imines via C-H Bond Functionalization[J]. Journal of the American Chemical Society,2011, 133(5):1248-1250. (b) Li Y, Li B J, Wang W H, et al. Rhodium-Catalyzed Direct Addition of Aryl C-H Bonds to N-Sulfonyl Aldimines[J]. Angewandte Chemie,2011,123(9):2163-2167.
[72]Zhou B, Yang Y, Li Y. Rhodium-catalyzed oxidative C2-acylation of indoles with aryl and alkyl aldehydes [J]. Chemical Communications,2012,48(42):5163-5165.
[73]Stuart D R, Bertrand-Laperle M, Burgess K M N, et al. Indole synthesis via rhodium catalyzed oxidative coupling of acetanilides and internal alkynes[J]. Journal of the American Chemical Society,2008,130(49):16474-16475.
[74]Chen J, Song G, Pan C L, et al. Rh(Ⅲ)-Catalyzed Oxidative Coupling of N-Aryl-2-aminopyridine with Alkynes and Alkenes[J]. Organic letters,2010,12(23):5426-5429.
[75]Stuart D R, Alsabeh P, Kuhn M, et al. Rhodium (Ⅲ)-catalyzed arene and alkene C-H bond functionalization leading to indoles and pyrroles [J]. Journal of the American Chemical Society, 2010,132(51):18326-18339.
[76]Huestis M P, Chan L, Stuart D R, et al. The Vinyl Moiety as a Handle for Regiocontrol in the Preparation of Unsymmetrical 2,3-Aliphatic-Substituted Indoles and Pyrroles [J]. Angewandte Chemie,2011,123(6):1374-1377.
[77]Wang C, Sun H, Fang Y, et al. General and Efficient Synthesis of Indoles through Triazene-Directed C-H Annulation [J]. Angewandte Chemie,2013,125(22):5907-5910.
[78](a) Liu B, Song C, Sun C, et al. Rhodium(III)-Catalyzed Indole Synthesis Using N-N Bond as an Internal Oxidant[J]. Journal of the American Chemical Society,2013,135(44):16625-16631. (b)Wang C, Huang Y. Traceless Directing Strategy:Efficient Synthesis of N-Alkyl Indoles via Redox-Neutral C-H Activation [J]. Organic letters,2013,15(20):5294-5297.
[79]Zhao D, Shi Z, Glorius F. Indole Synthesis by Rhodium(III)-Catalyzed Hydrazine-Directed C-H Activation:Redox-Neutral and Traceless by N-N Bond Cleavage [J]. Angewandte Chemie International Edition,2013,52(47):12426-12429.
[80]Rakshit S, Patureau F W, Glorius F. Pyrrole Synthesis via Allylic sp3 C- H Activation of Enamines Followed by Intermolecular Coupling with Unactivated Alkynes [J]. Journal of the American Chemical Society,2010,132(28):9585-9587.
[81]Li X, Gong X, Zhao M, et al. Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl) sulfonamides using activated and unactivated alkenes[J]. Organic letters,2011,13(21):5808-5811.
[82]Wang F, Song G, Li X. Rh(III)-Catalyzed Tandem Oxidative Olefination-Michael Reactions between Aryl Carboxamides and Alkenes[J]. Organic letters,2010,12(23):5430-5433.
[83]Zhu C, Falck J R. Rhodium catalyzed C-H olefination of N-benzoylsulfonamides with internal alkenes[J]. Chemical Communications,2012,48(11):1674-1676.
[84]Ryu T, Kim J, Park Y, et al. Rhodium-Catalyzed Oxidative Cyclization of Arylphosphonic Acid Monoethyl Esters with Alkenes:Efficient Synthesis of Benzoxaphosphole 1-Oxides [J]. Organic letters,2013,15(15):3986-3989.
[85]Du Y, Hyster T K, Rovis T. Rhodium (iii)-catalyzed oxidative carbonylation of benzamides with carbon monoxide[J]. Chemical Communications,2011,47(44):12074-12076.
[86]Zhu C, Xie W, Falck J R. Rhodium-Catalyzed Annulation of N-Benzoylsulfonamide with Isocyanide through C-H Activation[J].Chemistry-A European Journal,2011,17(45):12591-12595.
[87]Lian Y, Huber T, Hesp K D, et al. Rhodium (Ⅲ)-Catalyzed Alkenyl C-H Bond Functionalization:Convergent Synthesis of Furans and Pyrroles[J]. Angewandte Chemie International Edition,2013,52(2):629-633.
[88]Lian Y, Bergman R G, Ellman J A. Rhodium (Ⅲ)-catalyzed synthesis of phthalides by cascade addition and cyclization of benzimidates with aldehydes [J]. Chem. Sci.,2012,3(10):3088-3092.
[89]Lian Y, Bergman R G, Lavis L D, et al. Rhodium (Ⅲ)-Catalyzed Indazole Synthesis by C-H Bond Functionalization and Cyclative Capture [J]. Journal of the American Chemical Society,2013, 135(19):7122-7125.
[90]Yu D G, Suri M, Glorius F. RhⅢ/CuⅡ-Cocatalyzed Synthesis of 1H-Indazoles through C-H Amidation and N-N Bond Formation[J]. Journal of the American Chemical Society,2013,135(24): 8802-8805.
[91]Hyster T K, Ruhl K E, Rovis T. A Coupling of Benzamides and Donor/Acceptor Diazo Compounds To Form y-Lactams via Rh(III)-Catalyzed C-H Activation[J]. Journal of the American Chemical Society,2013,135(14):5364-5367.
[92](a) Liu G, Shen Y, Zhou Z, et al. Rhodium(III)-Catalyzed Redox-Neutral Coupling of N-Phenoxyacetamides and Alkynes with Tunable Selectivity [J]. Angewandte Chemie,2013, 125(23):6149-6153. (b) Zhu R, Wei J, Shi Z. Benzofuran synthesis via copper-mediated oxidative annulation of phenols and unactivated internal alkynes[J]. Chem. Sci.,2013,4(9):3706-3711.
[93](a) Ueura K, Satoh T, Miura M. An efficient waste-free oxidative coupling via regioselective C-H bond cleavage:Rh/Cu-catalyzed reaction of benzoic acids with alkynes and acrylates under air[J]. Organic letters,2007,9(7):1407-1409. (b) Ueura K, Satoh T, Miura M. Rhodium-and iridium-catalyzed oxidative coupling of benzoic acids with alkynes via regioselective CH bond cleavage [J]. The Journal of organic chemistry,2007,72(14):5362-5367.
[94](a) Morimoto K, Hirano K, Satoh T, et al. Synthesis of Isochromene and Related Derivatives by Rhodium-Catalyzed Oxidative Coupling of Benzyl and Allyl Alcohols with Alkynes[J]. The Journal of organic chemistry,2011,76(22):9548-9551. (b) Mochida S, Shimizu M, Hirano K, et al. Synthesis of naphtho [1,8-bc] pyran derivatives and related compounds through hydroxy group directed CH bond cleavage under rhodium catalysis [J]. Chemistry, an Asian journal,2010,5(4): 847-851. (c) Seo J, Park Y, Jeon I, et al. Synthesis of Phosphaisocoumarins through Rhodium-Catalyzed Cyclization Using Alkynes and Arylphosphonic Acid Monoesters[J]. Organic letters,2013,15(13):3358-3361. (d) Unoh Y, Hashimoto Y, Takeda D, et al. Rhodium(III)-catalyzed Oxidative Coupling through C-H Bond Cleavage Directed by Phosphinoxy Groups [J]. Organic letters,2013,15(13):3258-3261.
[95](a) Hyster T K, Rovis T. Rhodium-Catalyzed Oxidative Cycloaddition of Benzamides and Alkynes via C-H/N-H Activation[J]. Journal of the American Chemical Society,2010,132(30): 10565-10569. (b) Mochida S, Umeda N, Hirano K, et al. Rhodium-catalyzed Oxidative Coupling/Cylization of Benzamides with Alkynes via CH Bond Cleavage [J]. Chemistry Letters, 2010,39(7):744-746. (c) Song G, Chen D, Pan C L, et al. Rh-Catalyzed Oxidative Coupling between Primary and Secondary Benzamides and Alkynes:Synthesis of Polycyclic Amides [J]. The Journal of organic chemistry,2010,75(21):7487-7490.
[96]Hyster T K, Rovis T. An improved catalyst architecture for rhodium (Ⅲ) catalyzed C-H activation and its application to pyridone synthesis [J]. Chem. Sci.,2011,2(8):1606-1610.
[97]Guimond N, Gouliaras C, Fagnou K. Rhodium (Ⅲ)-Catalyzed Isoquinolone Synthesis:The N-O Bond as a Handle for C-N Bond Formation and Catalyst Turnover[J]. Journal of the American Chemical Society,2010,132(20):6908-6909.
[98]Xu X, Liu Y, Park C M. Rhodium (Ⅲ)-Catalyzed Intramolecular Annulation through C-H Activation:Total Synthesis of (±)-Antofine, (±)-Septicine,(±)-Tylophorine, and Rosettacin[J]. Angewandte Chemie,2012,124(37):9506-9510
[99]Guimond N, Gorelsky S I, Fagnou K. Rhodium (Ⅲ)-catalyzed heterocycle synthesis using an internal oxidant:improved reactivity and mechanistic studies [J]. Journal of the American Chemical Society,2011,133(16):6449-6457.
[100]Hyster T K, Knorr L, Ward T R, et al. Biotinylated Rh (Ⅲ) complexes in engineered streptavidin for accelerated asymmetric C-H activation[J]. Science,2012,338(6106):500-503.
[101]Ye B, Cramer N. Chiral Cyclopentadienyl Ligands as Stereocontrolling Element in Asymmetric C-H Functionalization [J]. Science,2012,338(6106):504-506.
[102](a) Davis T A, Hyster T K, Rovis T. Rhodium (Ⅲ)-Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck-type Reaction:Three Distinct Pathways Determined by an Amide Directing Group[J]. Angewandte Chemie International Edition,2013,52(52):14181-14185. (b) Shi Z, Boultadakis-Arapinis M, Koester D C, et al. Rh (Ⅲ)-Catalyzed Intramolecular Redox-Neutral Cyclization of Alkenes via CH Activation[J]. Chemical Communications,2014.
[103]Wang H, Glorius F. Mild Rhodium (Ⅲ)-Catalyzed C-H Activation and Intermolecular Annulation with Allenes [J]. Angewandte Chemie International Edition,2012,51(29):7318-7322.
[104]Wang H, Grohmann C, Nimphius C, et al. Mild Rh (Ⅲ)-Catalyzed C-H Activation and Annulation with Alkyne MIDA Boronates:Short, Efficient Synthesis of Heterocyclic Boronic Acid Derivatives [J]. Journal of the American Chemical Society,2012,134(48):19592-19595.
[105]Presset M, Oehlrich D, Rombouts F, et al. Complementary Regioselectivity in Rh (Ⅲ)-Catalyzed Insertions of Potassium Vinyltrifluoroborate via C-H Activation:Preparation and Use of 4-Trifluoroboratotetrahydroisoquinolones [J]. Organic letters,2013,15(7):1528-1531.
[106]Yu D G, de Azambuja F, Glorius F. a-MsO/TsO/Cl Ketones as Oxidized Alkyne Equivalents: Redox-Neutral Rhodium (Ⅲ)-Catalyzed C-H Activation for the Synthesis of N-Heterocycles [J]. Angewandte Chemie International Edition,2014,53(10):2754-2758.
[107]Guimond N, Fagnou K. Isoquinoline synthesis via rhodium-catalyzed oxidative cross-coupling/cyclization of aryl aldimines and alkynes [J]. Journal of the American Chemical Society,2009,131(34):12050-12051.
[108](a) Too P C, Wang Y F, Chiba S. Rhodium (Ⅲ)-catalyzed synthesis of isoquinolines from aryl ketone o-acyloxime derivatives and internal alkynes [J]. Organic letters,2010,12(24):5688-5691. (b) Zhang X, Chen D, Zhao M, et al. Synthesis of Isoquinolines via Rhodium (Ⅲ)-Catalyzed Dehydrative C-C and C-N Coupling between Oximines and Alkynes [J]. Advanced Synthesis & Catalysis,2011,353(5):719-723. (c) Hyster T K, Rovis T. Pyridine synthesis from oximes and alkynes via rhodium (iii) catalysis:Cp* and Cpt provide complementary selectivity [J]. Chemical Communications,2011,47(43):11846-11848. (d) Zhao D, Lied F, Glorius F. Rh (Ⅲ)-Catalyzed C-H Functionalization/Aromatization Cascade with 1,3-Dienes:A Redox-Neutral and Regioselective Access to Isoquinolines [J]. Chemical Science,2014.
[109]Wang Y F, Toh K K, Lee J Y, et al. Synthesis of Isoquinolines from a-Aryl Vinyl Azides and Internal Alkynes by Rh-Cu Bimetallic Cooperation[J]. Angewandte Chemie,2011,123(26): 6049-6053.
[110]Pham M V, Ye B, Cramer N. Access to Sultams by Rhodium (Ⅲ)-Catalyzed Directed C-H Activation[J]. Angewandte Chemie,2012,124(42):10762-10766.
[111]Dong W, Wang L, Parthasarathy K, et al. Rhodium-Catalyzed Oxidative Annulation of Sulfoximines and Alkynes as an Approach to 1,2-Benzothiazines[J]. Angewandte Chemie International Edition,2013,52(44):11573-11576.
[112]Lian Y, Hummel J R, Bergman R G, et al. Facile Synthesis of Unsymmetrical Acridines and Phenazines by a Rh (Ⅲ)-Catalyzed Amination/Cyclization/Aromatization Cascade [J]. Journal of the American Chemical Society,2013,135(34):12548-12551.
[113]Li G, Ding Z, Xu B. Rhodium-Catalyzed Oxidative Annulation of Sulfonylhydrazones with Alkenes[J]. Organic letters,2012,14(20):5338-5341.
[114]Shi Z, Koester D C, Boultadakis-Arapinis M, et al. Rh (Ⅲ)-Catalyzed Synthesis of Multisubstituted Isoquinoline and Pyridine N-Oxides from Oximes and Diazo Compounds [J]. Journal of the American Chemical Society,2013,135(33):12204-12207.
[115]Zhang G, Yang L, Wang Y, et al. An Efficient Rh/O2 Catalytic System for Oxidative C-H Activation/Annulation:Evidence for Rh (Ⅰ) to Rh (Ⅲ) Oxidation by Molecular Oxygen[J]. Journal of the American Chemical Society,2013,135(24):8850-8853.
[116]Shi Z, Grohmann C, Glorius F. Mild Rhodium (Ⅲ)-Catalyzed Cyclization of Amides with a, β-Unsaturated Aldehydes and Ketones to Azepinones:Application to the Synthesis of the Homoprotoberberine Framework [J]. Angewandte Chemie International Edition,2013,52(20): 5393-5397.
[117]Cui S, Zhang Y, Wu Q. Rh (iii)-catalyzed C-H activation/cycloaddition of benzamides and methylenecyclopropanes:divergence in ring formation [J]. Chemical Science,2013,4(9): 3421-3426.
[118]Cui S, Zhang Y, Wang D, et al. Rh (iii)-catalyzed C-H activation/[4+3] cycloaddition of benzamides and vinylcarbenoids:facile synthesis of azepinones[J]. Chemical Science,2013,4(10): 3912-3916.
[119](a) Seoane A, Casanova N, Quinones N, et al. Straightforward assembly of Benzoxepines by means of a Rhodium (Ⅲ)-Catalyzed CH Functionalization of ortho-vinylphenols [J]. Journal of the American Chemical Society,2013. (b) Yu S, Li X. Rhodium (Ⅲ)-Catalyzed C-C Coupling of Arenes with 2-Vinyloxiranes:Synthesis of Allylic Alcohols[J]. Organic letters,2014,16(4): 1200-1203.
[1]Wu X F, Anbarasan P, Neumann H, et al. From Noble Metal to Nobel Prize: Palladium-Catalyzed Coupling Reactions as Key Methods in Organic Synthesis [J]. Angewandte Chemie International Edition,2010,49(48):9047-9050.
[2](a) Fujiwara Y, Moritani I, Matsuda M, et al. Aromatic substitution of styrene-palladium chloride complex. Ⅱ effect of metal acetate [J]. Tetrahedron Letters,1968,9(5):633-636. (b) Moritani I, Matsuda M. Aromatic substitution of olefin-Ⅲ:Reaction of styrene-palladium (Ⅱ) chloride complex [J]. Tetrahedron,1968,24(13):4819-4824.
[3](a) Heck R F. Palladium-catalyzed reactions of organic halides with olefins[J]. Accounts of Chemical Research,1979,12(4):146-151. (b) Beletskaya I P, Cheprakov A V. The Heck reaction as a sharpening stone of palladium catalysis [J]. Chemical Reviews,2000,100(8):3009-3066.
[4](a) Xiao B, Fu Y, Xu J, et al. Pd (Ⅱ)-Catalyzed C-H Activation/Aryl-Aryl Coupling of Phenol Esters[J]. Journal of the American Chemical Society,2010,132(2):468-469. (b) Zhao X, Yeung C S, Dong V M. Palladium-catalyzed ortho-arylation of O-phenylcarbamates with simple arenes and sodium persulfate [J]. Journal of the American Chemical Society,2010,132(16):5837-5844.
[5]Yamazaki K, Kawamorita S, Ohmiya H, et al. Directed Ortho Borylation of Phenol Derivatives Catalyzed by a Silica-Supported Iridium Complex [J]. Organic letters,2010,12(18):3978-3981.
[6]Lattanzi A, Senatore A, Massa A, et al. Novel highly regioselective VO (acac)2/TBHP mediated oxidation of o-alkenyl phenols to o-hydroxybenzyl ketones [J]. The Journal of organic chemistry, 2003,68(9):3691-3694.
[7]Stuart D R, Bertrand-Laperle M, Burgess K M N, et al. Indole synthesis via rhodium catalyzed oxidative coupling of acetanilides and internal alkynes[J]. Journal of the American Chemical Society,2008,130(49):16474-16475.
[8]Feng C, Loh T P. Rhodium-catalyzed direct ortho C-H olefination of phenol derivatives[J]. Chemical Communications,2011,47(37):10458-10460.
[1](a) Ma S. Some typical advances in the synthetic applications of allenes[J]. Chemical reviews, 2005,105(7):2829-2872. (b) Ma S. Electrophilic addition and cyclization reactions of allenes[J]. Accounts of chemical research,2009,42(10):1679-1688. (c) Krause N, Winter C. Gold-catalyzed nucleophilic cyclization of functionalized allenes:a powerful access to carbo-and heterocycles[J]. Chemical reviews,2011,111(3):1994-2009. (d) Hoffmann-Roder A, Krause N. Enantioselective Synthesis of and with Allenes[J]. Angewandte Chemie International Edition,2002,41(16): 2933-2935. (e) Hashmi A S K, Stephen K. Modern allene chemistry[M]. Weinheim:Wiley-VCH, 2004.
[2]Zhang Y J, Skucas E, Krische M J. Direct Prenylation of Aromatic and α,β-Unsaturated Carboxamides via Iridium-Catalyzed C-H Oxidative Addition-Allene Insertion[J]. Organic letters, 2009,11(18):4248-4250.
[3]Tran D N, Cramer N. syn-Selective Rhodium (I)-Catalyzed Allylations of Ketimines Proceeding through a Directed C-H Activation/Allene Addition Sequence[J]. Angewandte Chemie International Edition,2010,49(44):8181-8184.
[4]Kuninobu Y, Yu P, Takai K. Rhenium-Catalyzed Diastereoselective Synthesis of Aminoindanes via the Insertion of Allenes into a C-H Bond [J]. Organic letters,2010,12(19):4274-4276.
[5](a) Wang H, Glorius F. Mild Rhodium (Ⅲ)-Catalyzed C-H Activation and Intermolecular Annulation with Allenes [J]. Angewandte Chemie International Edition,2012,51(29):7318-7322. (b) Zeng R, Fu C, Ma S. Highly selective mild stepwise allylation of N-methoxybenzamides with allenes [J]. Journal of the American Chemical Society,2012,134(23):9597-9600. (c) Ye B, Cramer N. A Tunable Class of Chiral Cp Ligands for Enantioselective Rhodium (Ⅲ)-Catalyzed C-H Allylations of Benzamides [J]. Journal of the American Chemical Society,2013,135(2):636-639.
[6](a) Back T G, Clary K N, Gao D. Cycloadditions and Cyclizations of Acetylenic, Allenic, and Conjugated Dienyl Sulfones [J]. Chemical reviews,2010,110(8):4498-4553. (b) Trost B M, Pinkerton A B, Seidel M. Ruthenium-catalyzed two-component addition to form 1,3-dienes: Optimization, scope, applications, and mechanism [J]. Journal of the American Chemical Society, 2001,123(50):12466-12476.
[1]Kleemann A, Engel J, Kutscher B, et al. Pharmaceutical substances:syntheses, patents, applications [M]. Stuttgart:Thieme,1999.
[2](a) Anbarasan P, Schareina T, Beller M. Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides:synthesis of benzonitriles [J]. Chemical Society Reviews,2011,40(10):5049-5067. (b) Kim J, Kim H J, Chang S. Synthesis of Aromatic Nitriles Using Nonmetallic Cyano-Group Sources [J]. Angewandte Chemie International Edition,2012, 51(48):11948-11959. (c) Ding S, Jiao N. N, N-Dimethylformamide:A Multipurpose Building Block[J]. Angewandte Chemie International Edition,2012,51(37):9226-9237.
[3]Sandmeyer T. Ueber die Ersetzung der Amidgruppe durch Chlor in den aromatischen Substanzen[J]. Berichte der deutschen chemischen Gesellschaft,1884,17(2):1633-1635.
[4]Rosenmund K W, Struck E. Das am ringkohlenstoff gebundene halogen und sein ersatz durch andere substituenten. I. mitteilung:ersatz des halogens durch die carboxylgruppe[J]. Berichte der deutschen chemischen Gesellschaft (A and B Series),1919,52(8):1749-1756.
[5]Takagi K, Okamoto T, Sakakibara Y, et al. Palladium (Ⅱ) catalyzed synthesis of aryl cyanides from aryl halides [J]. Chemistry Letters,1973 (5):471-474.
[6](a) Schareina T, Zapf A, Beller M. Potassium hexacyanoferrate (Ⅱ)-a new cyanating agent for the palladium-catalyzed cyanation of aryl halides [J]. Chemical Communications,2004 (12): 1388-1389. (b) Weissman S A, Zewge D, Chen C. Ligand-free palladium-catalyzed cyanation of aryl halides[J]. The Journal of organic chemistry,2005,70(4):1508-1510. (c) Schareina T, Zapf A, Beller M. An environmentally benign procedure for the Cu-catalyzed cyanation of aryl bromides[J]. Tetrahedron letters,2005,46(15):2585-2588. (d) Grossman O, Gelman D. Novel trans-spanned palladium complexes as efficient catalysts in mild and amine-free cyanation of aryl bromides under air[J]. Organic letters,2006,8(6):1189-1191. (e) Weining W L Z, Zheng D. Cyanation Reactions with Potassium Hexacyanoferrate (Ⅱ)[J]. Tetrahedron Lett,2007,48(7):1087-1090.
[7](a) Sawant D N, Wagh Y S, Tambade P J, et al. Cyanides-Free Cyanation of Aryl Halides using Formamide[J]. Advanced Synthesis & Catalysis,2011,353(5):781-787. (b) Kim J, Choi J, Shin K, et al. Copper-Mediated Sequential Cyanation of Aryl C-B and Arene C-H Bonds Using Ammonium Iodide and DMF [J]. Journal of the American Chemical Society,2012,134(5):2528-2531. (c) Kim J, Kim H, Chang S. Copper-Mediated Selective Cyanation of Indoles and 2-Phenylpyridines with Ammonium Iodide and DMF [J]. Organic letters,2012,14(15):3924-3927.
[8](a)Luo F H, Chu C I, Cheng C H. Nitrile-group transfer from solvents to aryl halides. Novel carbon-carbon bond formation and cleavage mediated by palladium and zinc species [J]. Organometallics,1998,17(6):1025-1030. (b) Jiang Z, Huang Q, Chen S, et al. Copper-Catalyzed Cyanation of Aryl Iodides with Malononitrile:An Unusual Cyano Group Transfer Process from C (sp3) to C (sp2)[J]. Advanced Synthesis & Catalysis,2012,354(4):589-592. (c) Zheng S, Yu C, Shen Z. Ethyl cyanoacetate:a new cyanating agent for the palladium-catalyzed cyanation of aryl halides[J]. Organic letters,2012,14(14):3644-3647. (d) Zhang G, Ren X, Chen J, et al. Copper-Mediated Cyanation of Aryl Halide with the Combined Cyanide Source[J]. Organic letters, 2011,13(19):5004-5007.
[9]Chen X, Hao X S, Goodhue C E, et al. Cu (Ⅱ)-Catalyzed Functionalizations of Aryl CH Bonds Using 02 as an Oxidant[J]. Journal of the American Chemical Society,2006,128(21):6790-6791.
[10]Kim J, Chang S. A New Combined Source of "CN" from N, N-Dimethylformamide and Ammonia in the Palladium-Catalyzed Cyanation of Aryl C-H Bonds[J]. Journal of the American Chemical Society,2010,132(30):10272-10274.
[11]Ding S, Jiao N. Direct Transformation of N, N-Dimethylformamide to-CN:Pd-Catalyzed Cyanation of Heteroarenes via C-H Functionalization[J]. Journal of the American Chemical Society, 2011,133(32):12374-12377.
[12]Anbarasan P, Neumann H, Beller M. A General Rhodium-Catalyzed Cyanation of Aryl and Alkenyl Boronic Acids[J]. Angewandte Chemie International Edition,2011,50(2):519-522. Anbarasan P, Neumann H, Beller M. For N-cyano-N-phenyl-p-toluenesulfonamide (NCTS), see[J]. Chem.Eur.J,2011,17:4217.
[13]Yang Y, Zhang Y, Wang J. Lewis Acid Catalyzed Direct Cyanation of Indoles and Pyrroles with N-Cyano-N-phenyl-p-toluenesulfonamide (NCTS) [J]. Organic letters,2011,13(20): 5608-5611.
[14]Young M B, Barrow J C, Glass K L, et al. Discovery and evaluation of potent P1 aryl heterocycle-based thrombin inhibitors[J]. Journal of medicinal chemistry,2004,47(12):2995-3008.
[1](a) Kochanowska-Karamyan A J, Hamann M T. Marine indole alkaloids:Potential new drug leads for the control of depression and anxiety[J]. Chemical reviews,2010,110(8):4489-4497. (b) Bandini M, Eichholzer A. Catalytic functionalization of indoles in a new dimension[J]. Angewandte Chemie International Edition,2009,48(51):9608-9644. (c) Arisawa M, Kasaya Y, Obata T, et al. Design and Synthesis of Indomethacin Analogues That Inhibit P-Glycoprotein and/or Multidrug Resistant Protein without Cox Inhibitory Activity[J]. Journal of medicinal chemistry,2012,55(18): 8152-8163.
[2](a) Cacchi S, Fabrizi G. Synthesis and functionalization of indoles through palladium-catalyzed reactions[J]. Chemical reviews,2005,105(7):2873-2920. (b) Humphrey G R, Kuethe J T. Practical methodologies for the synthesis of indoles[J]. Chemical reviews,2006,106(7):2875-2911. (c) Vicente R. Recent advances in indole syntheses:New routes for a classic target[J]. Organic & biomolecular chemistry,2011,9(19):6469-6480. (d) Inman M, Moody C J. Indole synthesis-something old, something new[J]. Chemical Science,2013,4(1):29-41.
[3]For Pd-catalyzed direct C-H indoles synthesis, see:(a) Tan Y, Hartwig J F. Palladium-Catalyzed Amination of Aromatic C-H Bonds with Oxime Esters[J]. Journal of the American Chemical Society, 2010,132(11):3676-3677. (b) Neumann J J, Rakshit S, Droege T, et al. Exploring the Oxidative Cyclization of Substituted N-Aryl Enamines:Pd-Catalyzed Formation of Indoles from Anilines[J]. Chemistry-A European Journal,2011,17(26):7298-7303. (c) Wei Y, Deb I, Yoshikai N. Palladium-Catalyzed Aerobic Oxidative Cyclization of N-Aryl Imines:Indole Synthesis from Anilines and Ketones[J]. Journal of the American Chemical Society,2012,134(22):9098-9101.
[4]For Rh-catalyzed direct C-H indoles synthesis, see:(a) Stuart D R, Bertrand-Laperle M, Burgess K M N, et al. Indole synthesis via rhodium catalyzed oxidative coupling of acetanilides and internal alkynes[J]. Journal of the American Chemical Society,2008,130(49):16474-16475. (b) Stuart D R, Alsabeh P, Kuhn M, et al. Rhodium (Ⅲ)-catalyzed arene and alkene C-H bond functionalization leading to indoles and pyrroles[J]. Journal of the American Chemical Society,2010,132(51): 18326-18339. (c) Huestis M P, Chan L, Stuart D R, et al. The Vinyl Moiety as a Handle for Regiocontrol in the Preparation of Unsymmetrical 2,3-Aliphatic-Substituted Indoles and Pyrroles [J]. Angewandte Chemie,2011,123(6):1374-1377.
[5]For Cu-catalyzed direct C-H indoles synthesis, for see:(a) Bernini R, Fabrizi G. Sferrazza A, et al. Copper-Catalyzed C-C Bond Formation through C-H Functionalization:Synthesis of Multisubstituted Indoles from N-Aryl Enaminones[J]. Angewandte Chemie,2009,121(43): 8222-8225. (b) Li Y M, Sun M, Wang H L, et al. Direct Annulations toward Phosphorylated Oxindoles:Silver-Catalyzed Carbon-Phosphorus Functionalization of Alkenes[J]. Angewandte Chemie International Edition,2013,52(14):3972-3976.
[6]For Ru-catalyzed direct C-H indoles synthesis, see:Zhang T, Wu L, Li X. Rh (Ⅲ)-Catalyzed Olefination of N-Sulfonyl Imines:Synthesis of Ortho-Olefinated Benzaldehydes[J]. Organic letters, 2013,15(24):6294-6297.
[7]For Fe-catalyzed direct C-H indoles synthesis, see:Guan Z H, Yan Z Y, Ren Z H, et al. Preparation of indoles via iron catalyzed direct oxidative coupling[J]. Chemical Communications, 2010,46(16):2823-2825.
[8]For Au-catalyzed direct C-H indoles synthesis, see:Wang Y, Ye L, Zhang L. Au-catalyzed synthesis of 2-alkylindoles from N-arylhydroxylamines and terminal alkynes[J]. Chemical Communications,2011,47(27):7815-7817.
[9]For Ni-catalyzed direct C-H indoles synthesis, see:Song W, Ackermann L. Nickel-catalyzed alkyne annulation by anilines:versatile indole synthesis by C-H/N-H functionalization[J]. Chemical Communications,2013,49(59):6638-6640.