Copper-Catalyzed Double Borylation of Silylacetylenes: Highly Regio- and Stereoselective Synthesis of Syn-Vicinal Diboronates

Phosphite-copper(I) complexes efficiently catalyzed the double borylation of internal silylated alkynes to provide vicinal diboronates with excellent regio- and stereoselectivity. The copper-catalyzed reaction between bis(pinacolato)diboron (B(2)pin(2)) and aryl-substituted silylacetylenes in the presence of MeOII resulted in double syn addition of the pinacolboronate moiety (Bpin) and H across the triple bond with complete selectivity. While the double borylation was highly efficient for aryl-substituted alkynylsilanes and silylacetylene, only monoborylation took place with alkyl-substituted alkynylsilanes to yield (Z)-(beta-borylvinyl)silanes under the developed catalytic conditions.