α,β‐Dehydrogenation Adjacent to Sulfur‐ and Phosphorus‐ Containing Compounds

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.