铜催化烯烃氰烷基化成环合成含氰吲哚酮

doi:10.11944/j.issn.1000-0518.2015.08.150005

摘要/Abstract

摘要：

发展一种简单、高效的铜催化活泼烯烃氰烷基化成环合成吲哚酮的方法。在CuI/DTBP(叔丁基过氧化物)催化作用下, N-芳基丙烯酰胺类化合物与α-氰基偶氮试剂发生自由基环化反应, 高效地合成了一系列含α-氰基季碳中心的吲哚酮, 并探讨了其反应机理。该方法底物适用范围较广、反应体系温和, 催化体系廉价。

关键词: α-氰偶氮试剂, 含氰吲哚酮, C—H环化, 自由基, 铜催化

Abstract:

A practical, mild and highly efficient cyanoalkylation reaction of activated alkenes by copper catalysis has been developed. In the presence of CuI/DTBP(Di-tert-butyl peroxide), N-arylacrylamide undergoes radical cyclization smoothly, and affords a series of pharmaceutically important oxindoles bearing an α-cyano quaternary carbon center. The protocol features broad substrate scope, simplicity of operation and handling, and inexpensive catalytic systems. In addition, the synthetic application and possible mechanism process in the cyclization reaction were also demonstrated.

Key words: polymer microgel, α-cyano azo compounds, cyano-containing oxindoles, C—H cyclization, radical, copper catalysis

中图分类号:

李志豪, 唐石, 周栋, 邓佑林, 李玉花, 黎淑华. 铜催化烯烃氰烷基化成环合成含氰吲哚酮[J]. 应用化学, 2015, 32(8): 884-891.

LI Zhihao, TANG Shi, ZHOU Dong, DENG Youlin, LI Yuhua, LI Shuhua. Copper-catalyzed Cyanoalkylation of Alkenes to Form Cyano-containing Oxindoles[J]. Chinese Journal of Applied Chemistry, 2015, 32(8): 884-891.

参考文献

[1]	Posner G H. Multicomponent One-pot Annulations Forming 3 to 6 Bonds[J]. Chem Rev, 1986, 86(5): 831-834.
[2]	Lu L Q, Chen J R, Xiao W J. Development of Cascade Reactions for the Concise Construction of Diverse Heterocyclic Architectures[J]. Acc Chem Res, 2012, 45(8): 1278-1293.
[3]	Mai W, Wang J, Yang L, et al.Progress in Synthesis of Oxindoles by Radical Addition-Cyclization[J]. Chinese J Org Chem, 2014, 14(10): 1958-1965.
[4]	Tang S, Zhou D, Deng Y, et al.Copper-catalyzed Meerwein Carboarylation of Alkenes with Anilines to Form 3-Benzyl-3-Alkyloxindole[J]. Sci China Chem, 2014, 58(4): 684-688.
[5]	Shen T, Yuan Y, Jiao N. Metal-Free Nitro-Carbocyclization of Activated Alkenes: A Direct Approach to Synthesize Oxindoles by Cascade C—N and C—C Bond Formation[J]. Chem Commun, 2014, 50(5): 554-556.
[6]	Zhou M, Song R, Ouyang X, et al.Metal-free Oxidative Tandem Coupling of Activated Alkenes with Carbonyl C(Sp2)-H Bonds and Aryl C(Sp2)-H Bonds using TBHP[J]. Chem Sci, 2013, 4(6): 2690-2694.
[7]	Ouyang X, Song R, Li J. Iron-Catalyzed Oxidative 1, 2-Carboacylation of Activated Alkenes with Alcohols: A Tandem Route to 3-(2-Oxoethyl)indolin-2-ones[J]. Eur J Org Chem, 2014, 2014(16): 3395-3401.
[8]	Dai Q, Yu J, Jiang Y, et al.The Carbomethylation of Arylacrylamides Leading to 3-Ethyl-3-Substituted Indolin-2-One by Cascade Radical Addition/Cyclization[J]. Chem Commun, 2014, 50(29): 3865-3867.
[9]	Zhou M, Wang C, Song R, et al.Oxidative 1, 2-Difunctionalization of Activated Alkenes with Benzylic C(sp3)-H Bonds and Aryl C(sp2)-H Bonds[J]. Chem Commun, 2013, 49(92): 10817-10819.
[10]	Chen J, Yu X, Xiao W. Tandem Radical Cyclization of N-Arylacrylamides: An Emerging Platform for the Construction of 3, 3-Disubstituted Oxindoles[J]. Synthesis, 2015, 47(5): 604-629.
[11]	Yu W, Sit W N, Lai K, et al.Palladium-Catalyzed Oxidative Ethoxycarbonylation of Aromatic C—H Bond with Diethyl Azodicarboxylate[J]. J Am Chem Soc, 2008, 130(11): 3304-3305.
[12]	Klein J, Taylor R. Transition-Metal-Mediated Routes to 3, 3-Disubstituted Oxindoles through Anilide Cyclisation[J]. Eur J Org Chem, 2011, 2011(34): 6821-6841.
[13]	Wu T, Mu X, Liu G S. Palladium-Catalyzed Oxidative Arylalkylation of Activated Alkenes: Dual C—H Bond Cleavage of an Arene and Acetonitrile[J]. Angew Chem Int Ed, 2011, 50(52): 12578-12581.
[14]	Li J, Wang Z, Wu N, et al.Radical Cascade Cyanomethylation of Activated Alkenes to Construct Cyano Substituted Oxindoles[J]. Chem Commun, 2014, 50(95): 15049-15051.
[15]	Pan C, Zhang H, Zhu C. Fe-promoted Radical Cyanomethylation/Arylation of Arylacrylamides to Access Oxindoles via Cleavage of the sp3C—H of Acetonitrile and the sp2C—H of the Phenyl Group[J]. Org Biomol Chem, 2015, 13(2): 361-364.
[16]	Tang S, Yu Q, Peng P, et al.Palladium-catalyzed Carbonylative Annulation Reaction of 2-(1-Alkynyl)benzenamines: Selective Synthesis of 3-(Halomethylene)indolin-2-ones[J]. Org Lett, 2007, 9(17): 3413-3416.
[17]	Tang S, Zhou D, Wang Y. Metal-Free Meerwein Carboarylation of Alkenes with Anilines: A Straightforward Approach to 3-Benzyl-3-alkyloxindoles[J]. Eur J Org Chem, 2014, 2014(17): 3656-3661.
[18]	Tang S, Li S, Zhou D, et al.Stereoselective C(sp3)—C(sp2) Negishi Coupling of (2-Amido-1-phenylpropyl)zinc Compounds Through the Steric Control of β-Amido Group[J]. Sci Chinese Chem, 2014, 56(9): 1293-1300.