经典试剂：钯催化碳-碳偶联反应中的新惊喜

Classical reagents: new surprises in palladium-catalyzed C--C coupling reactions.

作者信息

Lindhardt Anders T, Skrydstrup Troels

机构信息

The Center for Insoluble Protein Structures (inSPIN), Department of Chemistry and the Interdisciplinary Nanoscience Center, University of Aarhus, Langelandsgade, 140, 8000 Aarhus (Denmark), Fax: (+45) 8619-6199.

出版信息

Chemistry. 2008;14(29):8756-8766. doi: 10.1002/chem.200800608.

DOI:10.1002/chem.200800608

PMID:18506859

Abstract

From investigations on a relatively simple concept to identify conditions for promoting Mizoroki-Heck reactions with vinyl tosylates and phosphates, two serendipitous discoveries were made concerning new properties of palladium as a catalyst. In the first case, beta-hydride eliminations well known for alkyl metal complexes were found to be equally feasible with alkenyl metal compounds. And secondly, conditions were found for promoting intermolecular ene-yne couplings via a PdII-H intermediate. This coupling reactions represents an atom economical Mizoroki-Heck type reaction.

摘要

从对一个相对简单的概念进行研究以确定促进乙烯基甲苯磺酸酯和磷酸盐的 Mizoroki-Heck 反应的条件出发，关于钯作为催化剂的新特性有两项意外发现。在第一个案例中，烷基金属配合物中熟知的β-氢消除反应被发现对于烯基金属化合物同样可行。其次，发现了通过 PdII-H 中间体促进分子间烯炔偶联的条件。这种偶联反应代表了一种原子经济的 Mizoroki-Heck 型反应。