Visible-Light-Initiated Manganese Catalysis for C-H Alkylation of Heteroarenes: Applications and Mechanistic Studies

被引：150

作者：

Nuhant, Philippe ^{[1
]}

Oderinde, Martins S. ^{[1
]}

Genovino, Julien ^{[1
]}

Juneau, Antoine ^{[2
]}

Gagne, Yohann ^{[2
]}

Allais, Christophe ^{[1
]}

Chinigo, Gary M. ^{[1
]}

Choi, Chulho ^{[1
]}

Sach, Neal W. ^{[1
]}

Bernier, Louise ^{[1
]}

Fobian, Yvette M. ^{[1
]}

Bundesmann, Mark W. ^{[1
]}

Khunte, Bhagyashree ^{[1
]}

Frenette, Mathieu ^{[2
]}

Fadeyi, Olugbeminiyi O. ^{[1
]}

机构：

[1] Pfizer Med Design & Oncol Med Chem, 445 Eastern Point Rd, Groton, CT 06340 USA

[2] Univ Quebec, Dept Chim, Case Postale 8888,Succursale Ctr Ville, Montreal, PQ H3C 3P8, Canada

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 48期

基金：

加拿大自然科学与工程研究理事会;

关键词：

C-H alkylation; DFT studies; manganese; Minisci reaction; redox chemistry; LATE-STAGE FUNCTIONALIZATION; HETEROAROMATIC BASES; PHOTOREDOX CATALYSIS; RADICAL-ADDITION; DIMANGANESE DECACARBONYL; FLEXIBLE APPROACH; HETEROCYCLES; CARBONYL; HALIDES; SUBSTITUTIONS;

D O I：

10.1002/anie.201707958

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A visible-light-driven Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn-2(CO)(10), to generate alkyl radicals from alkyl iodides has been developed. This Minisci protocol is compatible with a wide array of sensitive functional groups, including oxetanes, sugar moieties, azetidines, tert-butyl carbamates (Boc-group), cyclobutanes, and spirocycles. The robustness of this protocol is demonstrated on the late-stage functionalization of complex nitrogen-containing drugs. Photophysical and DFT studies indicate a light-initiated chain reaction mechanism propagated by Mn-.(CO)(5). The rate-limiting step is the iodine abstraction from an alkyl iodide by Mn-.(CO)(5).

引用

页码：15309 / 15313

页数：5

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