Nickel‐Catalyzed Directed Hydroarylation of Alkynes with Boronic Acids.

A regio‐ and stereoselective nickel‐catalyzed hydroarylation of alkynes using propargylic carbamates as directing groups has been developed. The reaction proceeds under mild reaction conditions using arylboronic acids in the absence of base. A range of heterocycles and functional groups are tolerated under the reaction conditions, providing high yields of trisubstituted alkenes with control of olefin geometry. Stereoselective synthesis of trisubstituted alkenes using a nickel catalyst under mild reaction conditions is reported. A propargylic carbamate serves as a directing group. Products are allylic carbamates that can undergo further transformation, for example, by copper‐mediated allylic substitution [ABSTRACT FROM AUTHOR]