Dehydrative and Decarboxylative Coupling of Alkynoic Acids with Allylic Alcohols

Abstract A direct dehydroxylative and decarboxylative coupling between a large number of allylic alcohols and alkynoic acids was realized affording 1,4-enyne motifs in high efficiency. In this reaction, calcium-promoted C–OH bond cleavage was crucial, which facilitated the sequential ­decarboxylation, and thus enabled the palladium-catalyzed allyl­–alkynyl coupling, which occurred in an environmentally benign manner tolerating a wide variety of functional groups. This protocol has been successfully used in preparing anticancer active rooperol derivatives in gram scale.