Asymmetric Conjugate Addition of Vinyl Arene-Derived Chiral Benzylcopper Nucleophiles.

We report the copper-catalyzed asymmetric conjugate addition of vinyl arene-derived nucleophiles to α,ß-unsaturated diesters. Due to the high electrophilicity of α,ß-unsaturated diesters toward nucleophilic copper catalysts, inclusion of vinyl arenes as pronucleophiles is challenging due to chemoselectivity issues in a multicomponent reaction compared with those of other successful examples of dienes, allenes, and enynes. In this method, chemoselective in situ generation of a chiral benzylic copper intermediate and its stereoselective addition to α,ß-unsaturated diesters provided organoboron adducts with contiguous stereogenic centers with good levels of diastereoselectivity and enantioselectivity (≤85:15 diastereomeric ratio and 99% enantiomeric excess, respectively).

Asymmetric Synthesis of ß-Aminoboronates via Copper-Catalyzed Reductive Coupling of Vinyl Boronates with Imines.

We report a copper-catalyzed asymmetric reductive coupling of vinyl boronates with imines, which directly access enantiomerically enriched ß-aminoalkylboronates. Stereoselective addition of the in situ generated chiral α-borylalkyl copper to N-phosphinoyl imines provided target products in good yields with high diastereo- and enantioselectivity. Vinyl boronate with methylated acenaphthoquinone as a boron ligand was essential to efficiently spawn asymmetric products, and organic transformations of the boron moiety, along with the easily removable N-protecting group, proved their synthetic utility.