Total Synthesis of C-α-Mannosyl Tryptophan via Palladium-Catalyzed C-H Glycosylation

作     者：Quanquan Wang Yue Fu Wanjun Zhu Shuang An Qianyi Zhou Shou-Fei Zhu Gang He Peng Liu Gong Chen 

作者机构：State Key Laboratory and Institute of Elemento-Organic ChemistryCollege of ChemistryNankai UniversityTianjin 300071 Department of ChemistryUniversity of PittsburghPittsburghPA 15260 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2021年第3卷第6期

页      面：1729-1736页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：The experimental studies of this work were funded by NSFC-91753124 NSFC-21672105 NSFC-21421062 and NSFC-21725204 grants 

主　　题：C-glycoside C−H glycosylation palladium auxiliary adipokinetic hormone 

摘      要：The C2-α-mannosyl-tryptophan amino acid is produced by a unique posttranslational modification(PTM)of proteins and poses a significant synthetic challenge.A new strategy based on Pd-catalyzed auxiliary-directed remote C-H glycosylation of tryptophan was developed,which generates the C2-α-mannopyranose(Man)-Trp unit in a highly efficient and stereoselective *** functional theory(DFT)computational studies support a concerted oxidative addition mechanism for the stereospecific functionalization of a Pd(II)palladacycle intermediate with anα-mannosyl chloride *** utility of this method was demonstrated in the first total synthesis of insect C-glycopeptide hormone Cam-HrTH-I.