Re(I)-Catalyzed C-C and C-S Bonds Formation via Regioselective C(sp2)-H Hydroalkylation and Hydrothiolation

Abstract

A regioselective Re(I)-catalysed dual hydroalkylation strategy has been developed, featuring Markovnikov-selective O–C(sp²)–H functionalization of phenols and anti-Markovnikov hydroalkylation of thiophenols. Furthermore, various biologically important phenols also underwent efficient ortho-C(sp²)–H hydroalkylation under the optimised conditions. Additionally, a subsequent nucleophilic addition of thiols to styrene delivers linear sulfane derivatives. The developed protocols show broad versatility, enabling diverse transformations of the hydroalkylated products.