Photocatalytic Amine-Promoted Selective Hydrochlorination and sp3 C–O Acylation of Alkyne-Tethered Methyl Ethers with Aldehydes

We present a photoredox and alkylamine-assisted approach for the selective hydrochlorination and acylation of sp3 C–O bonds in alkynyl methyl ethers using aldehydes. This method leverages a cascade of radical processes─including chlorine radical addition, hydrogen atom transfer, in situ imine radical addition, and spin-center shift─to enable selective hydrochlorination of alkynes and the spontaneous cleavage of sp3 C–O bonds. The transformation accommodates a broad range of internal alkyne-tethered ethers and aldehydes, providing an efficient and streamlined pathway to chloro-alkenyl ketones. Utilizing only a photocatalyst, chloride, and propylamine under light irradiation, this strategy offers a practical and complementary alternative to previous sp3 C–O cleavage protocols.