Premium
Switching Pathways: Room‐Temperature Neutral Solvolysis and Substitution of Amides
Author(s) -
Hutchby Marc,
Houlden Chris E.,
Haddow Mairi F.,
Tyler Simon N. G.,
LloydJones Guy C.,
BookerMilburn Kevin I.
Publication year - 2012
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201107117
Subject(s) - solvolysis , steric effects , substituent , chemistry , amide , substitution (logic) , polar effect , electronic effect , nitrogen atom , mechanism (biology) , stereochemistry , medicinal chemistry , hydrolysis , organic chemistry , ring (chemistry) , computer science , philosophy , epistemology , programming language
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.