Total Synthesis of Starfish Cyclic Steroid Glycosides.Part 3,Formal Total Synthesis of Luzonicosides A and D  

作　　者：Dapeng Zhu Mingyu Geng Dacheng Shen Biao Yu 

机构地区：[1]State Key Laboratory of Bioorganic and Natural Products Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai,200032 China

出　　处：《Chinese Journal of Chemistry》2023年第8期903-908,共6页中国化学（英文版）

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).

摘　　要：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.

关 键 词：Cyclic starfish glycosides Gold(l)catalysis Glycosylation De novo synthesis STEROID 

分 类 号：O62[理学—有机化学]