† Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, and ‡NTU-CBC Crystallography Facility, Nanyang Technological University, Singapore 637371, Singapore
§ School of Chemistry, University of Edinburgh, Edinburgh EH9 3JJ, U.K.
J. Am. Chem. Soc., 2014, 136 (48), pp 16764–16767
DOI: 10.1021/ja509963m
Publication Date (Web): November 12, 2014
Copyright © 2014 American Chemical Society
Abstract
A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal σ-bond metathesis between an N–H bond of ammonia and an endocyclic P–N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.
コメント