Borostannylation of Alkynes and Enynes. Scope and Limitations of the Reaction and Utility of the Adducts

The utility of the hetero-bismetallating reagent 1,3-dimethyl-2-trimethylstannyl-2-bora-1,3-diazacyclopentane (1) has not been fully realized because of the hydrolytic instability of the products derived from catalyzed vicinal syn-additions to alkynes. The isolation of a variety of such adducts derived from alkynes (and also from hitherto unreported additions to 1,3-enynes) as stable boron pinacolates is reported. Examples of the applications of resulting products in tandem cross-coupling reactions and as dienes in Diels-Alder reactions are illustrated.