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 

机构地区：[1]State Key Laboratory and Institute of Elemento-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071 [2]Department of Chemistry,University of Pittsburgh,Pittsburgh,PA 15260

出　　处：《CCS Chemistry》2021年第6期1729-1736,共8页中国化学会会刊（英文）

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

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 fashion.Density 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 donor.The utility of this method was demonstrated in the first total synthesis of insect C-glycopeptide hormone Cam-HrTH-I.

关 键 词：C-GLYCOSIDE C−H glycosylation PALLADIUM AUXILIARY adipokinetic hormone 

分 类 号：O62[理学—有机化学]