In carbohydrate chemistry,the stereoselective synthesis of 1,2-cis-glycosides remains a formidable challenge.This complexity is comparable to the synthesis of 1,2-cis-β-D-mannosides,primarily due to the adverse anome...In carbohydrate chemistry,the stereoselective synthesis of 1,2-cis-glycosides remains a formidable challenge.This complexity is comparable to the synthesis of 1,2-cis-β-D-mannosides,primarily due to the adverse anomeric andΔ-2 effects.Over the past decades,to attainβ-stereoselectivity in D-rhamnosylation,researchers have devised numerous direct and indirect methodologies,including the hydrogen-bond-mediated aglycone delivery(HAD)method,the synthesis ofβ-D-mannoside paired with C6 deoxygenation,and the combined approach of 1,2-trans-glycosylation and C2 epimerization.This review elaborates on the advancements inβ-Drhamnosylation and its implications for the total synthesis of tiacumicin B and other physiologically relevant glycans.展开更多
基金This work was supported by the Natural Science Foundation of Henan Province(No.232300421374),the Science and Technology Research Project of Henan Province(No.222102310231)the Zhongjing Young Scientist Program of Henan University of Chinese Medicine(No.00104311-2022-1-1-70)+1 种基金the Open Project of Key Laboratory of Carbohydrate Chemistry and Biotechnology,Ministry of Education(No.KLCCB-KF202203)the China Postdoctoral Science Fund Project(No.2021M690936).
文摘In carbohydrate chemistry,the stereoselective synthesis of 1,2-cis-glycosides remains a formidable challenge.This complexity is comparable to the synthesis of 1,2-cis-β-D-mannosides,primarily due to the adverse anomeric andΔ-2 effects.Over the past decades,to attainβ-stereoselectivity in D-rhamnosylation,researchers have devised numerous direct and indirect methodologies,including the hydrogen-bond-mediated aglycone delivery(HAD)method,the synthesis ofβ-D-mannoside paired with C6 deoxygenation,and the combined approach of 1,2-trans-glycosylation and C2 epimerization.This review elaborates on the advancements inβ-Drhamnosylation and its implications for the total synthesis of tiacumicin B and other physiologically relevant glycans.
