Novel synthesis of (d,l)-cis-chrysanthemic acid involving α,α′-dibromination of 2,2,5,5-tetramethylcyclohexane-1,3-dione: application to the enantioselective synthesis of (1R)-cis-chrysanthemic acid

被引：2

作者：

Krief, Alain ^{[1
]}

Dumont, Willy ^{[1
]}

Kremer, Adrian ^{[1
]}

机构：

[1] Fac Univ Notre Dame Paix, Lab Chim Organ Synth, B-5000 Namur, Belgium

来源：

TETRAHEDRON LETTERS | 2009年 / 50卷 / 20期

关键词：

Pyrethroids; Ketone halogenation; Carbocyclization; Br-M exchange; H-M exchange; Isomerization; PHASE-TRANSFER CATALYSTS; ALPHA-AMINO-ACIDS; ASYMMETRIC-SYNTHESIS; SOFT ACIDS; BASES; ALKYLATION; DESIGN; HARD;

D O I：

10.1016/j.tetlet.2009.03.001

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

cis-Chrysanthemic acid has been prepared in a few steps from dimethyldimedone via dibromination at alpha positions of each carbonyl carbons. The trans-dibromide which is almost exclusively formed has been isomerized to its cis-stereoisomer by highly chemoselective tandem H/K-K/H exchanges involving potassium bases at low temperature (<-40 degrees C) Carbocyclization of the potassium enolate intermediate takes place at around -30 degrees C and Provide the bicyclo[3.1.0]-hexane skeleton. Lithiated bases behave differently and mainly lead to Br/M rather than to H/M exchange. We have been unsuccessful in using state of the art enantioselective metallation reactions to achieve the enantioselective synthesis of (1R)-cis-chrysanthemic acid using the disclosed strategy. This therefore still remains challenge. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：2398 / 2401

页数：4

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