Switching pathways: room-temperature neutral solvolysis and substitution of amides.

Authors :: Hutchby M
Houlden CE
Haddow MF
Tyler SN
Lloyd-Jones GC
Booker-Milburn KI
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2012 Jan 09; Vol. 51 (2), pp. 548-51. Date of Electronic Publication: 2011 Nov 30.
Publication Year :: 2012
Abstract: Stick or twist: By introducing steric hindrance at the nitrogen atom, stable linear amides bearing an electron-withdrawing α-substituent (Z = Ar, PhSO(2), P(O)(OR)(2), CN, or CO(2)R) 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.<br /> (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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