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A Test for Synergetic Captodative Radical Stabilization
Author(s) -
Birkhofer Hermann,
Hädrich Johannes,
Beckhaus HansDieter,
Rüchardt Christoph
Publication year - 1987
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198705731
Subject(s) - radical , reactivity (psychology) , chemistry , anomer , reaction rate constant , kinetics , medicinal chemistry , stereochemistry , organic chemistry , physics , medicine , alternative medicine , pathology , quantum mechanics
In contrast to predictions based on the concept of captodative radical stabilization , the rate constants k for the formation of the radicals 2 from 1 increase dramatically in the order 2a < 2b < 2c . This order of reactivity is not only determined by the different stabilization of the radicals 2 by the pair of substituents X/Y, but also by attractive (anomeric effect in la ) and repulsive ( 1c ) σ interactions in the ethane derivatives 1 ( a , X = Y = CH 3 O; b , X = CH 3 O, Y = CN; c , X = Y = CN).