Bromination of tri(isopropyl)boroxine and asymmetric synthesis of (2-cyano-3,3-dimethylcyclopropyl)boronic esters

Bromination of triisopropylboroxine to tris(1-bromo-1-methylethyl)boroxine is far more facile than α-bromination of sec-alkylboronic esters. Normal fluorescent room light is sufficient to initiate the free radical reaction, which can be carried out as a titration. The steric environment for replacement of the bromine by lithioacetonitrile and subsequent asymmetric insertion of a chloromethyl group into the carbonboron bond is more highly hindered than what has been studied previously, and the pinanediol ester proved to be the only useful chiral boronic ester in such circumstances. Cyclization of the cyano-substituted boronic ester to the corresponding cyclopropylboronic ester yielded a mixture of diastereomers, presumably the result of base-induced epimerization of the initially formed major isomer having the boronic ester and cyano groups trans.