Copper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic gem-Dichlorides

A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem-dichloride and provides chiral internal 1,5-dienes featuring (Z)-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate-ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the (Z)-alkenyl chloride.

Automated summary

A catalytic asymmetric reaction involving allyl copper species with allylic gem-dichloride is reported, providing high selectivity chiral internal 1,5-dienes with (Z)-configured alkenyl boronate and alkenyl chloride. The synthetic utility of the products is demonstrated by synthesizing optically active compounds. DFT calculations reveal noncovalent substrate-ligand interactions accounting for the selectivity outcome.