Synthesis of (-)-Cubebol by Face-Selective Platinum-, Gold-, or Copper-Catalyzed Cycloisomerization: Evidence of Chirality Transfer and Mechanistic Insights

被引：59

作者：

Fehr, Charles ^{[1
]}

Winter, Beat ^{[1
]}

Magpantay, Iris ^{[1
]}

机构：

[1] Firmenich Co, Corp R&D Div, CH-1211 Geneva 8, Switzerland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2009年 / 15卷 / 38期

关键词：

cycloisomerization; cyclopropanes; diastereoselectivity; homogeneous catalysis; natural products; PTCL2-MEDIATED CYCLOISOMERIZATION; 1,5-ENYNES; ENYNES; REARRANGEMENTS; CYCLIZATION; N-ENYNES; ACTIVATION; MIGRATION; EFFICIENT; ACCESS;

D O I：

10.1002/chem.200901292

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We describe in detail a direct, stereoselective synthesis of (-)-cubebol based on it Pt-, Au-, or Cu-catalyzed cycloisomerization in which control of the configuration of the propargylic center is essential for the facial selectivity. In addition, we show that cycloisomerization reactions of enantioenriched propargyl pivalates occur with substantial chirality transfer. We confirm it mechanism by means of cyclization followed by an [1,2]-acyl migration for the Pt- and the Au-catalyzed cycloisomerization. So far, no evidence supports that the Cu-catalyzed cycloisomerization follows the same reaction course.

引用

页码：9773 / 9784

页数：12

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