Tetrabi 型磷配体铑配合物催化的内烯烃高区域选择性异构化-羟胺甲基化反应。

Highly regioselective isomerization-hydroaminomethylation of internal olefins catalyzed by Rh complex with Tetrabi-type phosphorus ligands.

机构信息

College of Science, Northwest A & F University, Yangling, Shaanxi 712100, PR China.

出版信息

Org Lett. 2012 Jan 6;14(1):102-5. doi: 10.1021/ol202848a. Epub 2011 Dec 13.

DOI:10.1021/ol202848a

Abstract

A highly regioselective isomerization-hydroaminomethylation of internal olefins has been developed. A 95.3% amine selectivity and 36.2 n/i ratio were obtained for 2-octene with a Tetrabi ligand and Rh(acac)(CO)(2), and a TON of linear amine was achieved of 6837 with a 39.1 n/i ratio of amine. The m-CF(3)-Ph substituted ligand was the best of the applied Tetrabi-type phosphorus ligands for different internal olefins, as up to a 99.2% amine selectivity and 95.6 n/i ratio were obtained for 2-pentene.

摘要

发展了一种高区域选择性的内烯烃异构化-氢胺甲基化反应。使用 Tetrabi 配体和 Rh(acac)(CO)(2)，可以使 2-辛烯获得 95.3%的胺选择性和 36.2 的 n/i 比，TON 线性胺达到 6837，胺的 n/i 比为 39.1。对于不同的内烯烃，应用的 Tetrabi 型磷配体中，m-CF(3)-Ph 取代配体是最好的，因为对于 2-戊烯，可以获得高达 99.2%的胺选择性和 95.6 的 n/i 比。