Piñeiro-Suárez, MartínÁlvarez-Constantino, Andrés M.Fañanás-Mastral, Martín2023-11-032023-11-032023-04-10ACS Catalysis 2023 13 (8), 5578-55832155-5435http://hdl.handle.net/10347/31152A 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 chlorideeng© 2023 The Authors. Published by American Chemical SocietyAtribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/CopperAllylborationAsymmetric catalysisAllenesMultifunctional compoundsNoncovalent interactionsjournal article10.1021/acscatal.3c005362155-5435open access