Organocatalytic trans Phosphinoboration of Internal Alkynes.

ABSTRACT

We report the first trans phosphinoboration of internal alkynes. With an organophosphine catalyst, alkynoate esters and the phosphinoboronate Ph2 P-Bpin are efficiently converted into the corresponding trans-α-phosphino-ß-boryl acrylate products in moderate to good yield with high regio- and Z-selectivity. This reaction operates under mild conditions and demonstrates good atom economy, requiring only a modest excess of the phosphinoboronate. X-ray crystallography experiments allowed structural assignment of the unprecedented and densely functionalized (Z)-α-phosphino-ß-boryl acrylate products.