Photocatalytic carbanion generation from C-H bonds - reductant free Barbier/Grignard-type reactions

被引：42
作者：
Berger, Anna Lucia [1 ]
Donabauer, Karsten [1 ]
Koenig, Burkhard [1 ]
机构：
[1] Univ Regensburg, Inst Organ Chem, Fac Chem & Pharm, Univ Str 31, D-93053 Regensburg, Germany
来源：
CHEMICAL SCIENCE | 2019年 / 10卷 / 48期
基金：
欧洲研究理事会;
关键词：
ALKYLATION; FUNCTIONALIZATION; ACIDITIES; ALKENES;
D O I：
10.1039/c9sc04987h
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report a redox-neutral method for the generation of carbanions from benzylic C-H bonds in a photocatalytic Grignard-type reaction. The combination of photo- and hydrogen atom transfer (HAT) catalysis enables the abstraction of a benzylic hydrogen atom, generating a radical intermediate. This radical is reduced in situ by the organic photocatalyst to a carbanion, which is able to react with electrophiles such as aldehydes or ketones, yielding homobenzylic secondary and tertiary alcohols.
引用
收藏
页码：10991 / 10996
页数：6
相关论文
共 47 条
[1]   Acyl Radical Chemistry via Visible-Light Photoredox Catalysis [J].
Banerjee, Arghya ;
Lei, Zhen ;
Ngai, Ming-Yu .
SYNTHESIS-STUTTGART, 2019, 51 (02) :303-333
[2]  
Barbier P., 1899, CR HEBD ACAD SCI, V128, P110
[3]   EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].
BORDWELL, FG .
ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463
[4]   ACIDITIES OF ANILINES AND TOLUENES [J].
BORDWELL, FG ;
ALGRIM, D ;
VANIER, NR .
JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (10) :1817-1819
[5]   Hydrogen Atom Transfer (HAT): A Versatile Strategy for Substrate Activation in Photocatalyzed Organic Synthesis [J].
Capaldo, Luca ;
Ravelli, Davide .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2017, 2017 (15) :2056-2071
[6]   The medicinal chemist's toolbox for late stage functionalization of drug-like molecules [J].
Cernak, Tim ;
Dykstra, Kevin D. ;
Tyagarajan, Sriram ;
Vachal, Petr ;
Krska, Shane W. .
CHEMICAL SOCIETY REVIEWS, 2016, 45 (03) :546-576
[7]   COAL SOLUBILIZATION - PROMOTION OF THE C-ALKYLATION REACTION BY NORMAL-BUTYLLITHIUM AND POTASSIUM TERT-BUTOXIDE [J].
CHATTERJEE, K ;
MIYAKE, M ;
STOCK, LM .
ENERGY & FUELS, 1990, 4 (03) :242-248
[8]   Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3 C-H bonds [J].
Chu, John C. K. ;
Rovis, Tomislav .
NATURE, 2016, 539 (7628) :272-275
[9]   The direct arylation of allylic sp3 C-H bonds via organic and photoredox catalysis [J].
Cuthbertson, James D. ;
MacMillan, David W. C. .
NATURE, 2015, 519 (7541) :74-77
[10]   Guiding principles for site selective and stereoselective intermolecular C-H functionalization by donor/acceptor rhodium carbenes [J].
Davies, Huw M. L. ;
Morton, Daniel .
CHEMICAL SOCIETY REVIEWS, 2011, 40 (04) :1857-1869
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