Stereoretentive O-to-C rearrangement of vinyl acetals: Solvent cage effects as a stereocontrol element

被引：52

作者：

Zhang, YD ^{[1
]}

Reynolds, NT ^{[1
]}

Manju, K ^{[1
]}

Rovis, T ^{[1
]}

机构：

[1] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 33期

关键词：

D O I：

10.1021/ja026972j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Lewis acid-mediated rearrangement of chiral vinyl acetals may be induced to provide the product of stereoretention using Me3Al and BF3·OEt2 in concert. The selectivities obtained in this reaction (86:14 to 96:4) are complementary to that observed when relying on oxocarbenium facial bias to control the newly formed stereocenter. Evidence is presented that this reaction occurs by tight ion-pair binding in the solvent cage. The relay of C-O bond stereochemistry to a C-C bond stereocenter via ionic intermediates is an addition to similar established methods such as the Claisen rearrangement. Copyright © 2002 American Chemical Society.

引用

页码：9720 / 9721

页数：2

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