Carbanion stabilization by distal silyloxy groups. Origin of the high diastereoselectivity in the formation of quaternary centers with aryllead(IV) triacetate reagents

被引：13

作者：

Konopelski, JP ^{[1
]}

Lin, JZ ^{[1
]}

Wenzel, PJ ^{[1
]}

Deng, HB ^{[1
]}

Elliott, GI ^{[1
]}

Gerstenberger, BS ^{[1
]}

机构：

[1] Univ Calif Santa Cruz, Dept Chem & Biochem, Santa Cruz, CA 95064 USA

来源：

ORGANIC LETTERS | 2002年 / 4卷 / 23期

关键词：

D O I：

10.1021/ol026863+

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Derivatives of methyl 5-hydroxy-2-oxo-1-cyclohexanecarboxylate react with aryllead(IV) reagents in high yield and with wide variation in diastereoselectivity. Ab initio calculations are consistent with a heretofore unrecognized attraction between the carbanionic center of the beta-ketoester intermediate and the distal OSiR3 group. This attractive interaction stabilizes the silyl group in the axial conformation and leads to the excellent trans diastereoselection in the formation of quaternary centers.

引用

页码：4121 / 4124

页数：4

共 21 条

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