Bismuth radical catalysis in the activation and coupling of redox-active electrophiles

被引：46

作者：

Mato, Mauro ^{[1
]}

Spinnato, Davide ^{[1
]}

Leutzsch, Markus ^{[1
]}

Moon, Hye Won ^{[1
]}

Reijerse, Edward J. J. ^{[2
]}

Cornella, Josep ^{[1
]}

机构：

[1] Max Planck Inst Kohlenforsch, Mulheim, Germany

[2] Max Planck Inst Chem Energiekonvers, Mulheim, Germany

来源：

NATURE CHEMISTRY | 2023年 / 15卷 / 08期

基金：

欧洲研究理事会;

关键词：

MAIN-GROUP ELEMENTS; ESTERS; PHOTOREDOX; AMINATION; OXIDATION; HALIDES; AMINES;

D O I：

10.1038/s41557-023-01229-7

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Radical cross-coupling reactions represent a revolutionary tool to make C(sp(3))-C and C(sp(3))-heteroatom bonds by means of transition metals and photoredox or electrochemical approaches. However, the use of main-group elements to harness this type of reactivity has been little explored. Here we show how a low-valency bismuth complex is able to undergo one-electron oxidative addition with redox-active alkyl-radical precursors, mimicking the behaviour of first-row transition metals. This reactivity paradigm for bismuth gives rise to well-defined oxidative addition complexes, which could be fully characterized in solution and in the solid state. The resulting Bi(III)-C(sp(3)) intermediates display divergent reactivity patterns depending on the a-substituents of the alkyl fragment. Mechanistic investigations of this reactivity led to the development of a bismuth-catalysed C(sp(3))-N cross-coupling reaction that operates under mild conditions and accommodates synthetically relevant NH-heterocycles as coupling partners.

引用

页码：1138 / +

页数：9

共 47 条

[1] Radical Cage Effects: Comparison of Solvent Bulk Viscosity and Microviscosity in Predicting the Recombination Efficiencies of Radical Cage Pairs [J].