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Wagner–Meerwein Rearrangements in the Gas Phase: Anchimeric Assistance to Acid‐Induced Dissociation of Optically Active Phenylpropanols
Author(s) -
Speranza Maurizio,
Filippi Antonello
Publication year - 1999
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(19990301)5:3<834::aid-chem834>3.0.co;2-g
Subject(s) - chemistry , protonation , gas phase , dissociation (chemistry) , enthalpy , activation energy , propanol , photochemistry , entropy (arrow of time) , thermodynamics , organic chemistry , ion , physics , methanol
Activation entropy, rather than enthalpy , governs anchimeric assistance in gas‐phase water loss from O‐protonated ( S )‐1‐phenyl‐2‐propanol and ( S )‐2‐phenyl‐1‐propanol. Conformational factors and electrostatic interactions are responsible for a gas‐phase frontside phenyl‐group participation, with an activation energy lower than that of the competing backside participation (see diagram).