高价异双金属铱-锡配合物催化的苄醇二次苄基化反应。

Secondary benzylation with benzyl alcohols catalyzed by a high-valent heterobimetallic Ir-Sn complex.

作者信息

Podder Susmita, Choudhury Joyanta, Roy Sujit

机构信息

Organometallics & Catalysis Laboratory, Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India.

出版信息

J Org Chem. 2007 Apr 13;72(8):3129-32. doi: 10.1021/jo0625094. Epub 2007 Mar 17.

DOI:10.1021/jo0625094

PMID:17367192

Abstract

A highly efficient secondary benzylation procedure has been demonstrated using a high-valent heterobimetallic complex [Ir2(COD)2(SnCl3)2(Cl)2(mu-Cl)2] 1 as the catalyst in 1,2-dichloroethane to afford the corresponding benzylated products in moderate to excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also with oxygen (alcohol), nitrogen (amide and sulfonamide), and sulfur (thiol) nucleophiles. Mechanistic investigation showed the intermediacy of the ether in this reaction. An electrophilic mechanism is proposed from Hammett correlation.

摘要

已证明一种高效的二级苄基化方法，使用高价异双金属配合物[Ir2(COD)2(SnCl3)2(Cl)2(μ-Cl)2] 1作为催化剂，在1,2-二氯乙烷中以中等至优异的产率得到相应的苄基化产物。该反应不仅与碳亲核试剂（芳烃和杂芳烃）发生，还与氧（醇）、氮（酰胺和磺酰胺）和硫（硫醇）亲核试剂发生。机理研究表明该反应中醚的中间体存在。通过哈米特相关性提出了一种亲电机理。