Revisit of the phenol O-glycosylation with glycosyl imidates, BF3 center dot OEt2 is a better catalyst than TMSOTf

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	Revisit of the phenol O-glycosylation with glycosyl imidates, BF3 center dot OEt2 is a better catalyst than TMSOTf
	Li YL(李亚莉) ; Mo HP(莫华萍) ; Lian GY(连高焱) ; Yu B(俞飚)
刊名	Carbohydr. Res.
	2012
卷号	363 页码:14-22
ISSN号	0008-6215
其他题名	对糖基亚胺酯的酚糖苷化的重新审视: BF3?OEt2 是比TMSOTf更好的催化剂
通讯作者	俞飚
英文摘要	With BF3 center dot OEt2 as the catalyst, the glycosylation of phenols with glycosyl trichloroacetimidates (or N-phenyl trifluoroacetimidates) bearing 2-O-participating groups leads to the desired 1,2-trans-O-glycosides in generally excellent yields without formation of the 1,2-cis-anomers. However, with TMSOTf as the catalyst, the outcomes of the corresponding phenol O-glycosylation are highly dependent on the nucleophilicity of the phenols; less nucleophilic is the phenol, higher amounts of the 1,2-cis-O-glycoside together with more side-products are generated. 1,2-Orthoesters have been found to be the major products at a low temperature (< -70 degrees C) in all these phenol O-glycosylation reactions, which are transformed into the final products at a higher temperature. BF3 center dot OEt2 is an effective catalyst to promote the conversion of 1,2-orthoesters into the corresponding 1,2-trans-O-glycosides. However, the 1,2-orthoesters could be converted into the dioxolenium triflate and glycosyl triflate in the presence of TMSOTf, these intermediates which might be in equilibrium with the glycosyl oxocarbenium related species lead to the final mixture of the alpha/beta-O-glycosides and side-products. (C) 2012 Elsevier Ltd. All rights reserved.
学科主题	生命有机化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1016/j.carres.2012.09.025
语种	英语
WOS记录号	WOS:000310924600003
公开日期	2013-08-23
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/28575]
专题	上海有机化学研究所_生命有机化学国家重点实验室
推荐引用方式 GB/T 7714	Li YL,Mo HP,Lian GY,et al. Revisit of the phenol O-glycosylation with glycosyl imidates, BF3 center dot OEt2 is a better catalyst than TMSOTf[J]. Carbohydr. Res.,2012,363:14-22.
APA	李亚莉,莫华萍,连高焱,&俞飚.(2012).Revisit of the phenol O-glycosylation with glycosyl imidates, BF3 center dot OEt2 is a better catalyst than TMSOTf.Carbohydr. Res.,363,14-22.
MLA	李亚莉,et al."Revisit of the phenol O-glycosylation with glycosyl imidates, BF3 center dot OEt2 is a better catalyst than TMSOTf".Carbohydr. Res. 363(2012):14-22.