Switching Selectivity in Borylative Allyl–Allyl Cross-Coupling through Synergistic Catalysis

• DOI: 10.1021/jacs.4c07188
• Publication Date: 2024-07-24T17:49:30Z
• Authors: Nuria Vázquez-Gal...; Giuseppe Sciortino; Martín Piñeiro-Su...; Balázs L. Tóth; Feliu Maseras; Martín Fañanás-Ma...
• Keywords: Allyl Group; Inorganic Carbon Compounds; Selectivity; Stereoselectivity; Palladium

A 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.