Selective uni- and bidirectional homologation of diborylmethane.

Diborylmethane can be homologated uni- and bidirectionally by using enantiomerically pure lithium-stabilized carbenoids to give 1,2- and 1,3-bis(boronic esters), respectively, in good yield and with excellent levels of enantio- and diastereoselectivity. The high sensitivity of the transformation to steric hindrance enables the exclusive operation of either manifold, effected through the judicious choice of the type of carbenoid, which can be a sparteine-ligated or a diamine-free lithiated benzoate/carbamate. The scope of the 1,2-bis(boronic esters) so generated is complementary to that encompassed by the asymmetric diboration of alkenes, in that primary-secondary and primary-tertiary 1,2-bis(boronic esters) can be prepared with equally high levels of selectivity and that functional groups, such as terminal alkynes and alkenes, are tolerated. Methods for forming C2-symmetric and non-symmetrical anti and syn 1,3-bis(boronic esters) are also described and represent a powerful route towards 1,3-functionalized synthetic intermediates.

Highly diastereo- and enantioselective allylboration of aldehydes using α-substituted allyl/crotyl pinacol boronic esters via in situ generated borinic esters.

Readily available, α-substituted allyl/crotyl pinacol boronic esters often give low E/Z selectivity (with Z favored) in reactions with aldehydes. We found that addition of nBuLi to the pinacol boronic ester followed by trapping of the alkoxide with TFAA leads to an intermediate allyl borinic ester which undergoes allylboration with very high E selectivity. The substrate scope includes primary to tertiary alkyl α-substituents, crotyl substrates, and the previously unreported ß-methallyl pinacol boronic esters. The latter give very high Z selectivity under standard conditions which is completely reversed to high E selectivity under the new conditions. Monitoring the reaction by (11)B NMR confirmed that the reaction proceeds through a borinic ester intermediate.

Highly enantioselective synthesis of tertiary boronic esters and their stereospecific conversion to other functional groups and quaternary stereocentres.

Organoboron compounds are useful in asymmetric synthesis. We have developed an efficient methodology for the highly enantioselective synthesis of tertiary boronic esters from the corresponding secondary benzylic alcohols. Further stereospecific transformations of the boronic ester moiety are described including the preparation of tertiary alcohols, C-tertiary amines and tertiary arylalkanes. Several homologations of tertiary boronic esters have also been developed for the construction of quaternary stereocentres.