The first and asymmetric total syntheses of auriculatol D,micranthanoside IV,pierisformosides C,and I,glycosylated and highly unsaturated grayanoids,were achieved using a modular synthetic strategy.The glucosyls at C3...The first and asymmetric total syntheses of auriculatol D,micranthanoside IV,pierisformosides C,and I,glycosylated and highly unsaturated grayanoids,were achieved using a modular synthetic strategy.The glucosyls at C3-OH were selectively introduced via Wan glycosylation and Yu glycosylation,respectively.The tetracyclic architecture was assembled through a palladium-catalyzed coupling reaction and a lithiumhalogen exchange/intramolecular nucleophilic addition to the aldehyde sequence.The desaturation of the grayanoid core structure was achieved by the palladium-catalyzed elimination of an allylic ester.展开更多
基金the Science and Technology Major Program of Gansu Province of China(grant nos.22ZD6FA006,23ZDFA015,and 24ZD13FA017)the National Natural Science Foundation of China(grant nos.22322105 and 22071089)the Fundamental Research Funds for the Central Universities(grant no.lzujbky-2023-ey01).
文摘The first and asymmetric total syntheses of auriculatol D,micranthanoside IV,pierisformosides C,and I,glycosylated and highly unsaturated grayanoids,were achieved using a modular synthetic strategy.The glucosyls at C3-OH were selectively introduced via Wan glycosylation and Yu glycosylation,respectively.The tetracyclic architecture was assembled through a palladium-catalyzed coupling reaction and a lithiumhalogen exchange/intramolecular nucleophilic addition to the aldehyde sequence.The desaturation of the grayanoid core structure was achieved by the palladium-catalyzed elimination of an allylic ester.
