Combined Transition-Metal- and Organocatalysis: An Atom Economic C3 Homologation of Alkenes to Carbonyl and Carboxylic Compounds

被引：31

作者：

Kemme, Susanne T. ^{[1
]}

Smejkal, Tomas ^{[1
]}

Breit, Bernhard ^{[1
]}

机构：

[1] Univ Freiburg, Freiburg Inst Adv Studies, Inst Organ Chem & Biochem, D-79104 Freiburg, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 11期

关键词：

atom economy; hydroformylation; Knoevenagel condensation; organocatalysis; supramolecular catalysis; ACRYLONITRILE CROSS-METATHESIS; SYSTEMATIC SYNTHESIS DESIGN; STEREOSELECTIVE-SYNTHESIS; CATALYZED ADDITION; (E)-ALPHA; BETA-UNSATURATED ESTERS; STEREOSPECIFIC SYNTHESIS; KNOEVENAGEL REACTION; OLEFINATION REACTION; ORGANOBORONIC ACIDS; PRACTICAL SYNTHESIS;

D O I：

10.1002/chem.200903223

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A combination of regioselective room-temperature/ambient-pressure hydroformylation (transition-metal catalysis) and decarboxylative Knoevenagel reactions (organocatalysis) allowed for the development of an efficient, one-pot C3 homologation of terminal alkenes to (E)-alpha,beta-unsaturated acids and esters, (E)-beta,gamma-unsaturated acids, (E)-alpha-cyano acrylic acids, and alpha,beta-unsaturated nitriles. All reactions proceed under mild conditions, tolerate a variety of functional groups, and furnish unsaturated carbonyl compounds in good yields and with excellent regio- and stereocontrol. Further, an iterative C2 homologation of (E)-alpha,beta-unsaturated carboxylic acids is possible through a combination of decarboxylative hydroformylation employing a supramolecular catalyst followed by decarboxylative Knoevenagel condensation with an organocatalyst.

引用

页码：3423 / 3433

页数：11

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