Expanding the scope of C-H amination through catalyst design

Christine G Espino; Kristin Williams Fiori; Mihyong Kim; J Du Bois

doi:10.1021/ja0446294

Expanding the scope of C-H amination through catalyst design

J Am Chem Soc. 2004 Dec 1;126(47):15378-9. doi: 10.1021/ja0446294.

Authors

Christine G Espino¹, Kristin Williams Fiori, Mihyong Kim, J Du Bois

Affiliation

¹ Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.

PMID: 15563154
DOI: 10.1021/ja0446294

Abstract

Analysis of the mechanism for Rh-mediated C-H amination has led to the development of a remarkably effective dinuclear Rh catalyst derived from 1,3-benzenedipropionic acid. This unique complex, Rh2(esp)2, is capable of promoting both intra- and intermolecular C-H oxidation reactions, and in all cases is superior to Rh2(O2CtBu)4. For the first time, C-H insertion is described with urea and sulfamide substrates to give 1,2- and 1,3-diamine derivatives, respectively. In addition, intermolecular amination of benzylic and secondary C-H bonds is shown to proceed efficiently even under conditions in which the starting alkane is employed as the limiting reagent.