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

ABSTRACT: 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 S_E2' 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.

SUBMITTER: Vazquez-Galinanes N 

PROVIDER: S-EPMC11311230 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature