Development of a reductive Hosomi-Sakurai reaction

Herein we present a full account on the reductive Hosomi-Sakurai reaction along with some insight into the reaction mechanism. Stereoselectivity appears to be highest when the crucial carbocation intermediate, derived by protonation of the homoallylic ether, is sufficiently stabilized to ensure that the hydride transfer becomes rate-determining. This hypothesis is supported by experiment and mechanistic analysis.