An operationally simple approach to (E)-α-halo vinyl sulfides and their applications for accessing stereodefined trisubstituted alkenes

Abstract

An operationally simple and practical protocol for the synthesis of (E)-α-halo vinyl sulfides has been achieved via a highly regio- and stereoselective hydrohalogenation of alkynyl thioethers using lithium halides in HOAc or propionic acid at room temperature. It permits the formation of (E)-α-chloro and (E)-α-bromo vinyl sulfides in satisfactory yields with good to excellent stereoselectivities. Moreover, this work results in a new method for the assembly of stereodefined (E)- or (Z)-trisubstituted alkenes featuring the first coupling of the C–X bond of (E)-α-halo vinyl sulfides followed by a subsequent Ni-catalyzed coupling of the C–S bond with Grignard reagents.