Catalytic Access to Diastereometrically Pure Four‐ and Five‐Membered Silyl‐Heterocycles Using Transborylation

: Silyl-heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. The shortage of catalytic methods for the preparation of diverse and functionalized silyl-heterocycles however limits widespread exploration and exploitation. Herein the borane-catalyzed intramolecular 1,1-carboboration of silyl-alkynes has been developed for the synthesis of 2,3-dihydrosilolyl and silylcyclobut-2-enyl boronic esters. Successful, catalytic carboboration has been achieved on a variety of functionally diverse silyl-alkynes, using a borane catalyst and transborylation-enabled turnover. Mechanistic studies, including 13C-labelling, computational studies, and single-turnover experiments, suggest a reaction pathway proceeding by 1,2-hydroboration, 1,1-carboboration, and transborylation to release the alkenyl boronic ester product and regenerate the borane catalyst.