一种SeCSe-Pd(II)钳形配合物作为醛与烯丙基三丁基锡烯丙基化反应的高效催化剂。

A SeCSe-Pd(II) pincer complex as a highly efficient catalyst for allylation of aldehydes with allyltributyltin.

作者信息

Yao Qingwei, Sheets Matthew

机构信息

Department of Chemistry and Biochemistry, Michael Faraday Laboratories, Northern Illinois University, DeKalb, IL 60115-2862, USA.

出版信息

J Org Chem. 2006 Jul 7;71(14):5384-7. doi: 10.1021/jo060456k.

DOI:10.1021/jo060456k

PMID:16808533

Abstract

An air- and moisture-stable SeCSe-Pd(II) pincer complex was synthesized and found to catalyze the nucleophilic allylation of aldehydes with allyltributyltin. The allylation of a variety of aromatic and aliphatic aldehydes to give the corresponding homoallyl alcohols was performed at room temperature to 60 degrees C in yields ranging from 50% (for typical aliphatic aldehydes) to up to 97% (for aromatic aldehydes) using 5 x 10(-3) to 1 mol % of the Pd catalyst. NMR spectroscopic study indicated that a sigma-allylpalladium intermediate was formed and possibly functions as the nucleophilic species that undergoes addition to the aldehydes.

摘要

合成了一种对空气和湿气稳定的SeCSe-Pd(II)钳形配合物，并发现其能催化醛与烯丙基三丁基锡的亲核烯丙基化反应。在室温至60摄氏度下，使用5×10⁻³至1 mol%的钯催化剂，将各种芳香族和脂肪族醛进行烯丙基化反应，以得到相应的高烯丙醇，产率范围为50%（对于典型的脂肪族醛）至高达97%（对于芳香族醛）。核磁共振光谱研究表明，形成了一种σ-烯丙基钯中间体，并且可能作为亲核物种与醛发生加成反应。