α,β-Dehydrogenation Adjacent to Sulfur- and Phosphorus- Containing Compounds.

Abstract

Here, we report a robust nickel-catalyzed α,β-dehydrogenation process designed for substrates that contain electron-withdrawing sulfur and phosphorus groups. Leveraging the formation of organozinc intermediates and the utilization of a mild oxidant, allyl methyl carbonate, this methodology exhibits remarkable efficiency and outstanding diastereoselectivities across a diverse array of substrates, achieving E:Z ratios exceeding 20:1. Investigation through deuterium incorporation studies and an analysis of the reaction sequence leading to the formation of the dehydrogenative allylation side product, provide useful insights into reaction optimization.