Direct β-Alkylation of Aldehydes via Photoredox Organocatalysis

被引：176

作者：

Terrett, Jack A. ^{[1
]}

Clift, Michael D. ^{[1
]}

MacMillan, David W. C. ^{[1
]}

机构：

[1] Princeton Univ, Merck Ctr Catalysis, Princeton, NJ 08544 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 19期

关键词：

VISIBLE-LIGHT PHOTOCATALYSIS; CATALYSIS; ARYLATION; RADICALS; ACTIVATION; OXIDATION; KETONES; TRIFLUOROMETHYLATION; FUNCTIONALIZATION; STRATEGY;

D O I：

10.1021/ja502639e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Direct beta-alkylation of saturated aldehydes has been accomplished by synergistically combining photoredox catalysis and organocatalysis. Photon-induced enamine oxidation provides an activated beta-enaminyl radical intermediate, which readily combines with a wide range of Michael acceptors to produce beta-alkyl aldehydes in a highly efficient manner. Furthermore, this redox-neutral, atom-economical C-H functionalization protocol can be achieved both inter- and intramolecularly. Mechanistic studies by various spectroscopic methods suggest that a reductive quenching pathway is operable.

引用

页码：6858 / 6861

页数：4

共 39 条

[1] Synergistic catalysis: A powerful synthetic strategy for new reaction development [J].

Allen, Anna E. ;

MacMillan, David W. C. .

CHEMICAL SCIENCE, 2012, 3 (03) :633-658

[2] Estimation of standard reduction potentials of alkyl radicals involved in atom transfer radical polymerization [J].

Bortolamei, Nicola ;

Isse, Abdirisak A. ;

Gennaro, Armando .

ELECTROCHIMICA ACTA, 2010, 55 (27) :8312-8318

[3]

Bressy C., 2007, ENANTIOSELECTIVE ORG

[4]

Carey FA., 2007, ADV ORGANIC CHEM B

[5]

Evans D., 2006, ASYMMETRIC SYNTHESIS

[6] Photochemistry and photophysics of coordination compounds: Iridium [J].

Flamigni, Lucia ;

Barbieri, Andrea ;

Sabatini, Cristiana ;

Ventura, Barbara ;

Barigelletti, Francesco .

PHOTOCHEMISTRY AND PHOTOPHYSICS OF COORDINATION COMPOUNDS II, 2007, 281 :143-203

[7]

Fu ZQ, 2013, NAT CHEM, V5, P835, DOI [10.1038/NCHEM.1710, 10.1038/nchem.1710]

[8] Oxidative and Enantioselective Cross-Coupling of Aldehydes and Nitromethane Catalyzed by Diphenylprolinol Silyl Ether [J].

Hayashi, Yujiro ;

Itoh, Takahiko ;

Ishikawa, Hayato .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (17) :3920-3924

[9] Catalytic Direct β-Arylation of Simple Ketones with Aryl Iodides [J].

Huang, Zhongxing ;

Dong, Guangbin .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (47) :17747-17750

[10] Visible-light promoted bimetallic catalysis [J].

Inagaki, Akiko ;

Akita, Munetaka .

COORDINATION CHEMISTRY REVIEWS, 2010, 254 (11-12) :1220-1239

← 1 2 3 4 →