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

17 June 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Radical cross-coupling reactions represent a revolutionary tool to forge C(sp3)–C and C(sp3)–heteroatom bonds, by means of transition metals, photoredox or electrochemical approaches. This study demonstrates how a low-valent bismuth complex is able to undergo one-electron oxidative addition with redox-active alkyl radical precursors in an autonomous manner, mimicking the behavior of first-row transition metals. This reactivity paradigm for bismuth gives rise to unique radical-equilibrium complexes, which could be fully characterized in solution and solid state. The resulting Bi(III)–C(sp3) intermediates display divergent reactivity patterns depending on the α-substituents of the alkyl fragment. Mechanistic investigations on this reactivity led to the development of a bismuth-catalyzed C(sp3)–N cross-coupling reaction that operates under mild conditions and accommodates synthetically relevant N-heterocycles as coupling partners.


redox catalysis
C-N formation
Redox active esters

Supplementary materials

Bismuth radical catalysis in the activation and coupling of redox-active electrophiles. Supporting Information
Supporting information


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