Comprehensive Summary Luzonicosides A(1)and D(2)are the major saponins isolated from pacific starfish Echinaster Luzonicus,featuring a sterically congested 16-membered ring which is formed by bridging the C3 and C6 of...Comprehensive Summary Luzonicosides A(1)and D(2)are the major saponins isolated from pacific starfish Echinaster Luzonicus,featuring a sterically congested 16-membered ring which is formed by bridging the C3 and C6 of a 3β,6β-dihydroxy-Δ7-ene steroid with a 1,2-trans-linked linear trisaccharide via glycosidic and ether bonds,respectively.Here,we describe a formal total synthesis of starfish cyclic steroid glycosides 1 and 2.The synthetic route is highly modular and versatile,involving construction of the 16-membered macrocycles via Au(I)-catalyzed intramolecular glycosylation,highly efficient installation of unsaturated sugar moieties with ortho-hexynylbenzoates,elaboration of glucuronic acid unit via post-oxidation,and a de novo synthesis of the ether-linked pyranose unit.展开更多
基金the financial support from the National Natural Science Foundation of China(21901251)Shanghai Sailing Program(19YF1458400)Laboratory for Marine Drugs and Bioproducts of Qingdao National Laboratory for Marine Science andTechnology(LMDBKF201803).
文摘Comprehensive Summary Luzonicosides A(1)and D(2)are the major saponins isolated from pacific starfish Echinaster Luzonicus,featuring a sterically congested 16-membered ring which is formed by bridging the C3 and C6 of a 3β,6β-dihydroxy-Δ7-ene steroid with a 1,2-trans-linked linear trisaccharide via glycosidic and ether bonds,respectively.Here,we describe a formal total synthesis of starfish cyclic steroid glycosides 1 and 2.The synthetic route is highly modular and versatile,involving construction of the 16-membered macrocycles via Au(I)-catalyzed intramolecular glycosylation,highly efficient installation of unsaturated sugar moieties with ortho-hexynylbenzoates,elaboration of glucuronic acid unit via post-oxidation,and a de novo synthesis of the ether-linked pyranose unit.
