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1,3‐Benzyl Migration in Iminium Ions: Evidence for a Fast Free‐Radical Chain Reaction
Author(s) -
Blank Nancy,
Straub Bernd F.,
Opatz Till
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201101183
Subject(s) - chemistry , iminium , ion , chain reaction , thermochemistry , radical , radical ion , photochemistry , computational chemistry , organic chemistry , inorganic chemistry
The “exocyclic” 1,3‐benzyl shift observed in iminium salts derived from 1‐benzyl‐1,2,3,4‐tetrahydroisoquinolines is related to the “endocyclic” Knabe rearrangement. A crossover experiment, isotopic labelling, the study of initiators and inhibitors as well as DFT calculations of gas‐phase model structures provide evidence for a free‐radical pathway under kinetic entropy control that is not affected by “slow” radical traps.