铑催化的根岸烷基-芳基交叉偶联反应生成α-或β-磷酰基取代的烷基芳烃。

Rh-catalyzed Negishi alkyl-aryl cross-coupling leading to alpha- or beta-phosphoryl-substituted alkylarenes.

作者信息

Takahashi Hideki, Inagaki Shinya, Yoshii Naoko, Gao Fuxing, Nishihara Yasushi, Takagi Kentaro

机构信息

Department of Chemistry, Faculty of Science, Okayama University, Tsushima, Okayama 700-8530, Japan.

出版信息

J Org Chem. 2009 Apr 3;74(7):2794-7. doi: 10.1021/jo900142b.

DOI:10.1021/jo900142b

PMID:19267488

Abstract

The catalytic cross-coupling between ArZnX and ICH(2)(CH(2))(n)P(O)(OEt)(2) (n = 0-3) has been investigated to determine the utility of the Rh catalyst during the alkyl-aryl cross-coupling and to develop a new synthetic method for phosphoryl-substituted alkylarenes. Rh-dppf exhibits an excellent catalytic activity for the reaction with the alkylphosphonate of n = 1, whereas for the reaction with those of n = 2 or 3, beta-hydride elimination mainly takes place. As for the reaction with an alkylphosphonate of n = 0, a polarity inversion of the coupling components is necessary in order to provide the coupling products; the phosphoryl analogue of the Reformatsky reagent and ArI give the cross-coupling products in good yields through the catalysis by Rh-dppf.

摘要

研究了ArZnX与ICH(2)(CH(2))(n)P(O)(OEt)(2)（n = 0 - 3）之间的催化交叉偶联反应，以确定Rh催化剂在烷基 - 芳基交叉偶联中的效用，并开发一种合成磷酰基取代烷基芳烃的新方法。Rh - dppf对与n = 1的烷基膦酸酯的反应表现出优异的催化活性，而对于与n = 2或3的烷基膦酸酯的反应，主要发生β - 氢消除反应。至于与n = 0的烷基膦酸酯的反应，为了得到偶联产物，偶联组分需要进行极性反转；Reformatsky试剂的磷酰类似物与ArI通过Rh - dppf催化可高产率地得到交叉偶联产物。