NUCLEOPHILIC DISPLACEMENT REACTIONS IN CARBOHYDRATES .7. SOLVOLYSIS OF 3-O-BENZYL-1,2-O-ISOPROPYLIDENE-ALPHA-D-GLUCOFURANOSE 5,6-DISULPHONATES - FURTHER EXAMPLES OF BENZYLOXY-GROUP PARTICIPATION

被引:50
作者
BRIMACOMBE, JS
CHING, OA
机构
[1] The Chemistry Department, The University, P. O. Box 363
关键词
D O I
10.1016/S0008-6215(00)81693-6
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Solvolysis of the respective 3-O-benzyl-1,2-O-isopropylidene-α-D-glucofuranose 5,6-disulphonates in 50% aqueous methanol, in the presence of sodium acetate, afforded 3,6-anhydro-1,2-O-isopropylidene-5-O-toluene-p-sulphonyl-α-D-glucofuranose(5) and 3,6-anhydro-1,2-O-isopropylidene-5-O-methanesulphonyl-α-D-glucofuranose (6). 3-O-Benzyl-1,2-O-isopropylidene-5,6-di-O-methanesulphonyl-α-D-allofuranose (4) was synthesised and was found to be virtually unaffected in parallel experiments. The reactions leading to the 3,6-anhydro derivatives 5 and 6 are the result of neighbouring-group participation by the benzyloxy group, presumably in the rate-determining ionisation of the primary sulphonic ester groups, with formation and subsequent breakdown of the intermediate oxonium ions. © 1968.
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页码:82 / +
页数:1
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