Stereoselective alpha-sialylation with sialyl xanthate and phenylsulfenyl triflate as a promotor

被引：129

作者：

Martichonok, V ^{[1
]}

Whitesides, GM ^{[1
]}

机构：

[1] HARVARD UNIV,DEPT CHEM,CAMBRIDGE,MA 02138

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1996年 / 61卷 / 05期

关键词：

D O I：

10.1021/jo951711w

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reaction alpha- and beta-xanthates 2 and 3 of sialic acid with glycosyl accepters 5-8 in the presence phenylsulfenyl triflate (PST) as a promotor in a 2:1 mixture of CH3CN/CH2Cl2 at low temperature affords alpha-sialosides in good yield and stereoselectivity. PST is prepared in situ by reacting benzenesulfenyl chloride with silver triflate. Less reactive accepters 5 and 6 give a higher alp ratio than more reactive allylic alcohol 7 and primary alcohol 8; alpha-stereoselectivity is increased in a dilute solution. A possible mechanism of the reaction that involves intermediate alpha- and beta-nitrilium cations 16 and 17 is discussed.

引用

页码：1702 / 1706

页数：5

共 43 条

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