Asymmetric C-H oxidation of vic-diols to α-hydroxy ketones by a fructose-derived dioxirane:: Electronic effects on the enantioselectivity of oxygen transfer

被引:30
作者
Adam, W [1 ]
Saha-Möller, CR [1 ]
Zhao, CG [1 ]
机构
[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
关键词
D O I
10.1021/jo9907843
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A mechanistic study on the enantioselective C-H oxidation of vic-diols with the in-situ-generated dioxirane from the fructose-derived ketone 1 is presented. The asymmetrization of meso-configured and the kinetic resolution of racemic vie-diols 2 afforded the optically active alpha-hydroxy ketones 3 in opposite configurations with moderate to good ee values. Significant electronic effects on the enantioselectivity of C-H insertion have been observed, which are explained in terms of the hydrogen-bonded transition-state structures for the concerted C-H oxygen insertion.
引用
收藏
页码:7492 / 7497
页数:6
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