Rhodium-Catalysed Coupling of Allylic, Homoallylic, and Bishomoallylic Alcohols with Aldehydes and N-Tosylimines: Insights into the Mechanism

被引：38

作者：

Ahlsten, Nanna ^{[1
]}

Martin-Matute, Belen ^{[1
]}

机构：

[1] Stockholm Univ, Dept Organ Chem, Arrhenius Lab, S-10691 Stockholm, Sweden

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2009年 / 351卷 / 16期

基金：

瑞典研究理事会;

关键词：

aldehydes; allylic alcohols; isomerization; rhodium; N-tosylmines; REDUCTIVE ALDOL REACTION; MANNICH-TYPE REACTIONS; SITU OLEFIN MIGRATION; C BOND FORMATION; CARBONYL-COMPOUNDS; ISOMERIZATION; KETONES; CONDENSATION; ALPHA; CYCLIZATIONS;

D O I：

10.1002/adsc.200900448

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The isomerisation of alkenols followed by reaction with aldehydes or N-tosylimines catalysed by rhodium complexes has been studied. The catalytically active rhodium complex is formed in situ from commercially available (cyclooctadiene)rhodium(l) chloride dimer [Rh(COD)Cl](2). The tandem process affords aldol and Mannich-type products in excellent yields. The key to the success of the coupling reaction is the activation of the catalysts by reaction with postassium tert-butoxide (t-BuOK), which promotes a catalytic cycle via alkoxides rather than rhodium hydrides. This mechanism minimises the formation of unwanted by-products. The mechanism has been studied by H-1 NMR spectroscopy and deuterium labelling experiments.

引用

页码：2657 / 2666

页数：10

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