Research ArticlePHYSICAL SCIENCES

In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis

+ See all authors and affiliations

Science Advances  09 Aug 2017:
Vol. 3, no. 8, e1700826
DOI: 10.1126/sciadv.1700826

You are currently viewing the abstract.

View Full Text

Abstract

Although azides have been widely used in nitrene transfer reactions, in situ generation of N-H imines from azides for downstream transformations has rarely been explored. We report copper-mediated formation of N-unsubstituted aliphatic imines from easily available aliphatic azides using a customized phenanthroline-based ligand (L1*). Through trapping in situ–generated N-H imines, multisubstituted pyridines or indoles were readily synthesized. 13C-labeled azide was used as part of an isotope labeling study, which suggests that the construction of pyridine derivatives involves a three-component dehydrogenative condensation. The construction of 2,3,5-triaryl pyridines using this method provided evidence supporting a proposed pathway involving both imine formation and abnormal Chichibabin pyridine synthesis. The generation of N-unsubstituted imine intermediates was also confirmed by formation of indole derivatives from alkyl azides.

This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

View Full Text