An efficient synthetic method for preparing enantioenriched secondary borylalkanes has been achieved through a copper-catalyzed regio- and enantioselective hydroallylation of alkenyl boronates and boramides employing hydrosilanes and allylic phosphates. In the presence of a copper catalyst with a chiral Walphos ligand, a range of alkenylboron compounds with an aryl, heteroaryl, or alkyl substituent produced secondary homoallylic alkylboron compounds in good yields and with high enantioselectivities up to 99% ee. The utility of the resulting alkylboronates was demonstrated in an efficient synthesis of (S)-massoialactone.

An efficient, catalytic method for accessing tetrasubstituted enynylboronates has been established via copper-catalyzed chemo-, regio-, and stereoselective borylalkynylation of internal alkynes. In this protocol, a range of symmetrical and unsymmetrical internal alkynes with aryl, heteroaryl, and alkyl substituents afforded fully substituted enynylboron compounds in good yields and with high levels of regio- and stereoselectivity, up to a ratio of >20:1. The enynylboron products could be further utilized in transforming the C-B bond into C-C bonds by coupling reactions.

A copper-catalyzed, enantioselective method for the borylallylation of vinyl arenes is reported. The reaction produces enantioenriched and functionalized organoboron compounds by sequentially incorporating boryl and allyl groups onto the C═C bond of vinyl arenes. Copper-catalyzed borylative coupling of vinyl arenes with allyl phosphates successfully proceeds in a regio- and enantioselective manner in the absence of a palladium cocatalyst.

Copper-catalyzed enantioselective coupling of vinyl arenes with bis(pinacolato)diboron (B2pin2) and propargylic phosphates is presented.

Highly enantioselective, copper-catalyzed ring opening of bicyclic hydrazines using a diboron reagent was accomplished with (R,R)-taniaphos as a chiral ligand. Desymmetrization of various bicyclic hydrazines by boryl substitution afforded 3-Bpin-4-hydrazino-cyclopentene derivatives with enantioselectivity up to >99% under mild conditions. The resulting allylic boron products were utilized in further organic transformations. Kinetic resolution of a racemic bicyclic oxazine gave useful information about the relative rates of C–O and C–N bond cleavage.