Radical C(sp3)-H Functionalization and Cross-coupling Reactions

Overview

Journal Nat Rev Chem

Publisher Springer Nature

Specialty Chemistry

Date 2022 Aug 15

PMID 35965690

Authors

Dung L Golden

Sung-Eun Suh

Shannon S Stahl

Affiliations

Soon will be listed here.

Abstract

C─H functionalization reactions are playing an increasing role in the preparation and modification of complex organic molecules, including pharmaceuticals, agrochemicals, and polymer precursors. Radical C─H functionalization reactions, initiated by hydrogen-atom transfer (HAT) and proceeding via open-shell radical intermediates, have been expanding rapidly in recent years. These methods introduce strategic opportunities to functionalize C(sp)─H bonds. Examples include synthetically useful advances in radical-chain reactivity and biomimetic radical-rebound reactions. A growing number of reactions, however, proceed via "radical relay" whereby HAT generates a diffusible radical that is functionalized by a separate reagent or catalyst. The latter methods provide the basis for versatile C─H cross-coupling methods with diverse partners. In the present review, highlights of recent radical-chain and radical-rebound methods provide context for a survey of emerging radical-relay methods, which greatly expand the scope and utility of intermolecular C(sp)─H functionalization and cross coupling.

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