Doyle-Kirmse Reaction on Alkynyl Hydrazone Carboxylates: Synthesis of 1,4-Allenyne and 1,5-Enyne Thioaryl Carboxylates.

Abstract

The first Doyle-Kirmse reaction on alkynyl diazoacetates using allyl/propargyl sulfides is reported. The development provides diversified 1,5-enyne and 1,4-allenyne thioaryl carboxylates in good yields under ligand-/additive-free AuCl and Rh2(OAc)4 catalysis, respectively (48 examples, up to 96% yield). The study demonstrated the dual role of allyl sulfide as a ligand and substrate. Also, we have exemplified various synthetic modifications of the products to showcase the utility of different functional groups.