Visible-Light-Activated Catalytic Enantioselective β-Alkylation of α, β-Unsaturated 2-Acyl Imidazoles Using Hantzsch Esters as Radical Reservoirs

被引：55

作者：

de Assis, Francisco F. ^{[1
,2
]}

Huang, Xiaoqiang ^{[2
]}

Akiyama, Midori ^{[3
]}

Pilli, Ronaldo A. ^{[1
]}

Meggers, Eric ^{[2
]}

机构：

[1] Univ Estadual Campinas, Inst Quim, BR-13084971 Campinas, SP, Brazil

[2] Philipps Univ Marburg, Fachbereich Chem, Hans Meerwein Str 4, D-35043 Marburg, Germany

[3] Univ Tokyo, Grad Sch Engn, Dept Chem & Biotechnol, Tokyo, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 18期

基金：

巴西圣保罗研究基金会;

关键词：

LEWIS-ACID CATALYSIS; COUPLED ELECTRON-TRANSFER; PHOTOREDOX CATALYSIS; CONJUGATE ADDITION; FUNCTIONALIZATION; 4-ALKYL-1,4-DIHYDROPYRIDINES; DEBROMINATION; GENERATION; REAGENTS; KETONES;

D O I：

10.1021/acs.joc.8b01588

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An efficient and practical method for the enantioselective beta-functionalization of alpha, beta-unsaturated 2-acyl imidazoles is described. The method uses a previously devised chiral-at-metal rhodium catalyst (Lambda-RhS, 4 mol %) along with Hantzsch ester derivatives as alkyl radical sources. The rhodium complex exerts a dual role as the visible-light-absorbing unit upon substrate binding and as the asymmetric catalyst. The method provides up to quantitative yields with excellent enantioselectivities up to 98% ee and can be classified as a redox-neutral, electron-transfer-catalyzed reaction.

引用

页码：10922 / 10932

页数：11

共 29 条

[1] Catalytic enantioselective pyrrole alkylations of α,β-unsaturated 2-acyl imidazoles
Evans, David A.
Fandrick, Keith R.
ORGANIC LETTERS, 2006, 8 (11) : 2249 - 2252
[2] Catalytic Enantioselective Oxidative Homocoupling of 2-Acyl Imidazoles
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Qin, Jie
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[3] Rhodium(III)/Amine Synergistically Catalyzed Enantioselective Alkylation of Aldehydes with α,β-Unsaturated 2-Acyl Imidazoles
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[4] Catalytic Enantioselective α-Fluorination of 2-Acyl Imidazoles via Iridium Complexes
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Liang, Hui
Fang, Jie
Jia, Zhi-Long
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Xu, Peng-Fei
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[5] Enantioselective Conjugate Addition of Boronic Acids to α,β-Unsaturated 2-Acyl Imidazoles Catalyzed by Chiral Diols
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[6] Direct radical alkylation and acylation of 2H-indazoles using substituted Hantzsch esters as radical reservoirs
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Jiang, Pengxing
Liu, Yongguo
Du, Hongguang
Tan, Jiajing
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[7] Iron-Catalyzed Highly Enantioselective Addition of Silyl Enol Ethers to α,β-Unsaturated 2-Acyl Imidazoles
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[8] An enantioselective sulfa-Michael addition of alkyl thiols to α,β-unsaturated 2-acyl imidazoles catalyzed by a bifunctional squaramide
Jha, Rupesh K.
Rout, Subhrajit
Joshi, Harshit
Das, Arko
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[9] Rhodium(iii)/amine synergistically catalyzed enantioselective Michael addition of cyclic ketones with ,-unsaturated 2-acyl imidazoles
Qurban, Saira
Gong, Jun
Du, Yu
Kang, Qiang
ORGANIC CHEMISTRY FRONTIERS, 2018, 5 (19): : 2870 - 2874
[10] Enantioselective, Catalytic Trichloromethylation through Visible-Light-Activated Photoredox Catalysis with a Chiral Iridium Complex
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Wang, Chuanyong
Harms, Klaus
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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (30) : 9551 - 9554

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