C-glycosides by aqueous condensation of β-dicarbonyl compounds with unprotected sugars

被引：79

作者：

Riemann, I ^{[1
]}

Papadopoulos, MA ^{[1
]}

Knorst, M ^{[1
]}

Fessner, WD ^{[1
]}

机构：

[1] TH Darmstadt, Dept Organ Chem, D-64287 Darmstadt, Germany

来源：

AUSTRALIAN JOURNAL OF CHEMISTRY | 2002年 / 55卷 / 1-2期

关键词：

D O I：

10.1071/CH02012

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Condensation of 1, 3-diketones with unprotected aldoses in water, under mildly alkaline conditions, provides a convenient and effective route to C-glycosidic ketones in high yields. Reactions usually proceed with high beta-'anomeric' stereoselectivity because product composition is determined by thermodynamic control. Mechanistically, the condensation follows a typical Knoevenagel scheme, after which an intramolecular oxa-Michael cyclization determines C-glycoside configuration by following an exo- or endo-trig pathway. With open-chain 1,3-diketones, an ensuing retro-Claisen fragmentation occurs to furnish simple glycosyl monoketones. The C-glycosides then slowly further dehydrate under the reaction conditions to give 2, 5-disubstituted furans.

引用

页码：147 / 154

页数：8

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