We thank AstraZeneca and the EPSRC for the joint organic studentship initiative (M.H.) and the EPSRC for a grant to K.I.B.-M. and C.E.H (grant number EP/G036764/1). G.C.L.-J. is holder of a Royal Society Wolfson Research Merit Award.
Switching Pathways: Room-Temperature Neutral Solvolysis and Substitution of Amides†
Article first published online: 30 NOV 2011
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 51, Issue 2, pages 548–551, January 9, 2012
How to Cite
Hutchby, M., Houlden, C. E., Haddow, M. F., Tyler, S. N. G., Lloyd-Jones, G. C. and Booker-Milburn, K. I. (2012), Switching Pathways: Room-Temperature Neutral Solvolysis and Substitution of Amides . Angew. Chem. Int. Ed., 51: 548–551. doi: 10.1002/anie.201107117
- Issue published online: 4 JAN 2012
- Article first published online: 30 NOV 2011
- Manuscript Received: 7 OCT 2011
- EPSRC. Grant Number: EP/G036764/1
- steric hindrance;
- substituent effects;
Stick or twist: By introducing steric hindrance at the nitrogen atom, stable linear amides bearing an electron-withdrawing α-substituent (Z=Ar, PhSO2, P(O)(OR)2, CN, or CO2R) can be induced to undergo solvolysis and substitution reactions through an elimination–addition mechanism (see picture). Key to this process is a low barrier to rotation around the amide bond and the α-substituent Z.