B(C6F5)3-Mediated Transformations and Hydrogenation of Carbodiimides

被引：14

作者：

Holthausen, Michael H. ^{[1
]}

Colussi, Mariah ^{[1
]}

Stephan, Douglas W. ^{[1
]}

机构：

[1] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 05期

基金：

加拿大自然科学与工程研究理事会;

关键词：

amidines; carbodiimides; cyanamides; frustrated Lewis pairs; hydrogenation; FRUSTRATED LEWIS PAIRS; FREE CATALYTIC-HYDROGENATION; METAL-FREE HYDROGENATION; SUBSTITUTED BORON HALIDES; ASYMMETRIC HYDROGENATION; BOND ACTIVATION; IMINES; COMPLEXES; CHEMISTRY; ALKENES;

D O I：

10.1002/chem.201405014

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity of a series of carbodiimides RN=C=NR (R= tBu (1a), iPr (1b), SiMe3 (1c), and Dipp (2,6-di-iso-propylphenyl (1d)) with B(C6F5)(3) was investigated. After initial adduct formation, several distinct reaction pathways were identified. These pathways involve either isomerization of the carbodiimide to cyanamide derivatives or insertion of a carbodiimide into a B-C bond of B(C6F5)(3) to yield four-membered heterocycles. In the presence of dihydrogen, stepwise hydrogenation of the heteroallene moiety in the carbodiimides was achieved, which yielded the respective amidine-B(C6F5)(3) adducts and amidinium borate salts upon reaction with one or two equivalents of H-2, respectively.

引用

页码：2193 / 2199

页数：7