糖基
化学
立体选择性
烷基
组合化学
烯烃纤维
糖苷
催化作用
表面改性
糖基化
糖基供体
反应性(心理学)
另一个
有机化学
亲核细胞
自由基环化
作者
Yi Jiang,Quanquan Wang,Xinglong Zhang,Ming Joo Koh
出处
期刊:Chem
[Elsevier]
日期:2021-10-12
被引量:2
标识
DOI:10.1016/j.chempr.2021.09.008
摘要
Summary C-Alkyl glycosides occur widely in nature and are indispensable in drug development programs, owing to their diverse range of medicinal properties. Previous synthetic efforts often utilize stoichiometric reagents, and catalytic methods that afford such glycosides exhibit limited scope. Here, we describe a stereoselective Ti-catalyzed regime that efficiently merges a vast array of readily available glycosyl chlorides with activated olefins, through stereocontrolled glycosyl radical addition to deliver an assortment of C-alkyl glycosides. By employing alkynes as radical acceptors, the present strategy is amenable to the synthesis of C-alkenyl glycosides bearing a Z olefin appendage. The unexpected greater reactivity of glycosyl chlorides (compared with simple tertiary chloroalkanes) in the presence of an organotitanium complex is elucidated through mechanistic and computational studies. Utility of the protocol is underscored by the concise preparation of therapeutically important carbohydrates and glycopeptide conjugates, which are difficult to access using alternative approaches.
科研通智能强力驱动
Strongly Powered by AbleSci AI