Photoredox Catalysis for Building C–C Bonds from C(sp2)–H Bonds

Abstract

Transition metal-catalyzed C–H bond functionalizations have been the focus of intensive research over the last decades for the formation of C–C bonds from unfunctionalized arenes, heteroarenes, alkenes. These direct transformations provide new approaches in synthesis with high atom- and step-economy compared to the traditional catalytic cross-coupling reactions. However, such methods still suffer from several limitations including functional group tolerance and the lack of regioselectivity. In addition, they often require harsh reaction conditions and some of them need the use of strong oxidant, in a stoichiometric amount, avoiding these processes to be truly eco-friendly. The use of photoredox catalysis has contributed to a significant expansion of the scope of C(sp 2 )–H bond functionalizations which include the direct arylations, (perfluoro)alkylations, acylations, and even cyanations. Most of these transformations involve the photochemical induced generation of a radical followed by its regioselective addition to arenes, heteroarenes, or alkenes, leading to the building of a new C(sp 2 )–C bond. The use of photoredox catalysis plays crucial roles in these reactions promoting electron transfer, enabling the generation of radical species and single electron either oxidation or reduction. Such reactions operating at room temperature allow the building of C–C bonds with high chemo-, regio-, or stereoselectivity. This review surveys the formation of C(sp 2 )–C bonds initiated by photoredox catalysis which involves a C(sp 2 )–H bond functionalization step, describes the advantages compared to traditional C(sp 2 )–H bond functionalizations, and presents mechanistic insights into the role played by the photoredox catalysts.