Herein, we report the catalytic 1,6‐addition of chiral alkyl copper nucleophiles, in‐situ generated from borylalkenes and a copper‐hydride catalyst under mild conditions. Chemo‐ and stereoselective control was crucial in this reductive coupling process of borylalkenes and para‐quinone methides, sequentially forming adjacent stereogenic centers with good diastereo‐ and enantioselectivity. Through the multicomponent and catalytic tandem reactions, asymmetric 1,6‐adducts of p‐quinone methides were efficiently synthesized.

We report a ligand-free copper-catalyzed 1,6-addition of αborylalkyl copper species, catalytically generated from gemdiborylalkanes to para-quinone methides. The reaction proceeds with good yield for a variety of para-quinone methides and substituted gem-diborylalkanes with a catalytic amount of CuI as catalyst. This catalytic system provides a cost-effective process with good functional group tolerance under mild conditions.