Rhodium‐Catalysed Enantioselective C–H Functionalization in Asymmetric Synthesis

In this review, recent advances in the utilization of two classes of rhodium catalysts – namely rhodium(I) and rhodium(III) – in complexation with chiral cyclopentadienyl and phosphorus ligands in inter‐ and intramolecular asymmetric C–H bond activation/functionalization of aromatic and vinylic compounds is discussed. Because Rh complexes have been shown to be excellent catalysts for enantioselective alkylation, olefination and allylation of π systems through directed C–H functionalization under very mild conditions, this method has been seen to have broad synthetic potential both in organic chemistry and in biological systems. Moreover, selective conversion of ubiquitous C–H bonds into functional groups without intermediate preactivation is useful for shortening reaction sequences, with high environmental and economic benefits.