Synthesis of beta,beta-disubstituted vinyl boronates via the ruthenium-catalyzed Alder ene reaction of borylated alkynes and alkenes.

Ruthenium-catalyzed Alder ene reactions between borylated alkynes and terminal alkenes give the corresponding beta,beta-disubstituted vinyl boronates with high selectivity for the branched isomer. The stereochemistry of the vinyl boronate moiety was the result of a formal trans addition of the ene subunit across the alkyne, which is the opposite stereochemical outcome observed for other internal alkynes.