This article is published in Journal of Physical Organic Chemistry as a special issue on 13th European Symposium on Organic Reactivity edited by Peeter Burk (University of Tartu, Institute of Chemistry, 2 Jakobi St., Tartu, 51014, Estonia) and Marie-Francoise Ruasse (Université Paris VII-CNRSItODYS, ITODYS, 15 rue Jean de Baïf, 75205 PARIS CEDEX 13, PARIS, 75205, France).
Reactivity of nucleophiles toward a p-benzyne derived from an enediyne
Article first published online: 24 JUL 2012
Copyright © 2012 John Wiley & Sons, Ltd.
Journal of Physical Organic Chemistry
Special Issue: 13th European Symposium on Organic Reactivity
Volume 26, Issue 2, pages 206–210, February 2013
How to Cite
Perrin, C. L. and Reyes-Rodríguez, G. J. (2013), Reactivity of nucleophiles toward a p-benzyne derived from an enediyne. J. Phys. Org. Chem., 26: 206–210. doi: 10.1002/poc.2994
Presented by C. L. Perrin at ESOR XIII, September 2011, Tartu, Estonia.
- Issue published online: 25 JAN 2013
- Article first published online: 24 JUL 2012
- Manuscript Accepted: 12 JUN 2012
- Manuscript Revised: 5 JUN 2012
- Manuscript Received: 19 MAR 2012
- NSF. Grant Number: CHE07-42801
- NSF Instrumentation. Grant Number: CHE97-09183
- ACS-PRF. Grant Number: 48388-AC4
- NSF GK-12 STEM Fellows in Education Grant (to G. J. R.-R.), under NSF. Grant Number: 0742551
- nucleophilic addition;
Enediynes undergo cycloaromatization to p-benzyne diradicals. A new reaction of p-benzynes is here presented. Instead of their usual radical reactivity, they add nucleophiles, followed by protonation. Kinetic evidence showed that the rate-limiting step is the cycloaromatization, followed by rapid addition of a nucleophile. The unusual feature of nucleophilic addition to a radical center in a singlet diradical is discussed. Calculations that ignore solvation suggest that the addition has no activation barrier, but one is created by the necessity for desolvation of the anionic nucleophile. Relative reactivities of several nucleophiles have been measured under competition conditions. The observation of deuterium incorporation from DMSO-d6 or CD3CN shows that the species that is protonated is the aryl anion, not the p-benzyne. The extent of deuterium incorporation increases as the nucleophile is changed from iodide to bromide to chloride. This remarkable instance of selectivity is discussed. These studies of p-benzyne reactivity are exploring the nonradical chemistry of this diradical. Copyright © 2012 John Wiley & Sons, Ltd.