Synergizing palladium with Lewis base catalysis for stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates

•Synergistic palladium/Lewis base catalysis •Stereodivergent construction of vicinal stereocenters •100% atom-economical and additive-free coupling reaction •Concise access to all four stereoisomers with high diastereo- and enantio-selectivity Asymmetric coupling of 1,3-dienes with carbonyl compounds is one of the most powerful tools for atom-economical construction of the Csp3–Csp3 bond. Although many methods have been established for the coupling of 1,3-dienes, stereodivergent variants remain a formidable challenge because of their innate stereoselective bias (syn- or anti-) in a single catalyst system. Herein, we report a synergistic Pd/Lewis-base-catalyzed stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates. All four stereoisomers of the coupling products could be selectively obtained from the same pair of substrates simply by varying the relative chirality of the two catalysts. Coupled with the late-stage transformation of the pentafluorophenyl moiety, this method provides a general method to prepare various chiral molecules bearing vicinal stereocenters. Asymmetric coupling of 1,3-dienes with carbonyl compounds is one of the most powerful tools for atom-economical construction of the Csp3–Csp3 bond. Although many methods have been established for the coupling of 1,3-dienes, stereodivergent variants remain a formidable challenge because of their innate stereoselective bias (syn- or anti-) in a single catalyst system. Herein, we report a synergistic Pd/Lewis-base-catalyzed stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates. All four stereoisomers of the coupling products could be selectively obtained from the same pair of substrates simply by varying the relative chirality of the two catalysts. Coupled with the late-stage transformation of the pentafluorophenyl moiety, this method provides a general method to prepare various chiral molecules bearing vicinal stereocenters. Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-oneXu et al.ChemMay 2, 2022In BriefA dual-metal-catalyzed asymmetric stereodivergent allylic alkylation of benzofuran-3(2H)-ones has been developed by using a chiral N,N′-dioxide-Co(or Ni) complex and a phosphoramidite-Ir complex as catalysts. Stereodivergent total synthesis of eight rocaglaol stereoisomers was concisely achieved for further anticancer activity evaluation to understand stereochemical structure-activity relationships (SARs). Full-Text PDF Open Archive