Copper-Catalyzed 1,1-Boroalkylation of Terminal Alkynes: Access to Alkenylboronates via a Three-Component Reaction.

A copper-catalyzed three-component reaction of terminal alkynes, diazo compounds, and B2pin2 to prepare trisubstituted alkenylboronates has been developed. This difunctionalization of alkynes selectively occurs at the terminal carbon atom and proceeds via a tandem sequence. The copper catalyst plays dual roles in the whole process, namely, the initial copper-catalyzed cross-coupling and the following copper-catalyzed stereoselective boration reaction. Typically, different carbene precursors selectively lead to Z- and E-alkenes.