An Anomeric Base-Tolerant Ester of 8-Alkynyl-1-naphthoate for Gold(I)-Catalyzed Glycosylation Reaction  

作　　者：Xiaojuan Zhang Peng Xu Zhengbing Zhou Yazhou Zhang Biao Yu Yugen Zhu 

机构地区：[1]Zhongshan Institute for Drug Discovery,Shanghai Institute of Materia Medica,Chinese Academy of Sciences,Zhongshan,Guangdong,528400 China [2]Key Laboratory of Medicinal Chemistry for Natural Resource,Ministry of Education,Yunnan Provincial Center for Research&Development of Natural Products,School of Chemical Science and Technology,Yunnan University,Kunming,Yunnan,650091 China [3]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11期1305-1312,共8页中国化学（英文版）

基　　金：the financial support from the National Natural Science Foundation of China(22007080);Zhongshan Science and Technology Bureau(CXTD2022012);Youth Innovation Promotion Association of CAS(2020258);grateful to Hi-Level New R&D Institute(2019B090904008);High-Level Innovative Research Institute(2021B0909050003)from Department of Science;Technology of Guangdong Province.Prof.Hongbin Zhang(Yunnan University)is appreciated for the assistance on this project.

摘　　要：Given the extreme complexity and diversity of carbohydrates,efficient approaches to the homogeneous oligosaccharide remain limited.Chemical synthesis represents one of the most reliable methods to access homogeneous samples,which mainly relies on the key glycosylation reaction.Consistent with enormous efforts to develop leaving groups for establishing robust glycosylation protocols,we herein disclose a structurally novel leaving group of 8-phenylethynyl-1-naphthoate that is able to enable efficient glycosylation reactions under the extremely mild condition of gold(I)-catalysis.Notably,the anomeric naphthoate possesses the unprecedent character of base-stability in sharp contrast to the conventional ester groups at anomeric position of carbohydrates,which endows high compatibility with a variety of chemical transformations.Furthermore,the present glycosylation protocol with 8-phenylethynyl-1-naphthoate as leaving group is able to realize minimally protected glycosylation processes.Mechanistic studies reveal a unique structure of 8-phenylethynyl-1-naphthoate that accounts for the reason for these characteristics.

关 键 词：GLYCOSYLATION Leaving Group Gold Catalysis Anomeric Ester Base Tolerant Carbohydrates 

分 类 号：O62[理学—有机化学]