Premium
An AM 1 study of the coupling reaction of radicals with the acetone enolate ion and some related nucleophiles
Author(s) -
Pierini A. B.,
Borosky G. L.,
Baumgartner M. T.
Publication year - 1992
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560440507
Subject(s) - chemistry , radical , nucleophile , reactivity (psychology) , exothermic reaction , acetone , regioselectivity , solvent , medicinal chemistry , solvent effects , photochemistry , ion , computational chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert ‐butyl ≅ bicyclo‐[2.2.1]hept‐1‐yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc.