Site-Selective γ-Trihalomethylation and γ-Dihalomethylidenation of Silyl Dienol Ethers under Organophotoredox Catalysis.

Abstract

We report a general remote tribromo- and trichloromethylation process using CBr4 and CBrCl3 as ready available sources of trihalomethyl radicals. This method operates under mild and metal-free photocatalyzed conditions and enables the access to γ-trihalomethylated enals with complete regioselectivity in up to 71% isolated yield. Importantly, this protocol is easily adapted to the selective one-pot synthesis of the corresponding γ-dihalomethylidenated enals in up to 49% overall yield. Mechanistic studies are in favor of a radical chain propagation initiated by an oxidative quenching of the photocatalyst.