Vázquez-Galiñanes, NuriaSciortino, GiuseppePiñeiro-Suárez, MartínTóth, Balázs L.Maseras, FeliuFañanás-Mastral, Martín2025-02-212025-02-212024-07-24Nuria Vázquez-Galiñanes, Giuseppe Sciortino, Martín Piñeiro-Suárez, Balázs L. Tóth, Feliu Maseras, and Martín Fañanás-Mastral Journal of the American Chemical Society 2024 146 (31), 21977-21988 DOI: 10.1021/jacs.4c071880002-7863https://hdl.handle.net/10347/39822A Cu/Pd-catalyzed borylative coupling of allenes with allyl carbonates is reported. Synergistic Cu/Pd catalysis enables a divergent selectivity compared to Cu catalysis and allows for the regio-, diastereo-, and enantioselective formation of synthetically versatile chiral borylated 1,5-dienes featuring two adjacent tertiary stereocenters. DFT calculations support a closed inner-sphere SE2′ transmetalation between the catalytic allyl copper and allyl palladium intermediates and point at the reductive elimination of the resulting bis(allyl)Pd intermediate as the regio- and diastereo-determining step.eng© 2024 The Authors. Published byAmerican Chemical SocietyAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/Allyl GroupInorganic Carbon CompoundsPalladiumSelectivityStereoselectivityjournal article10.1021/jacs.4c071881520-5126open access