Premium
Solvolysis of isodrin derivatives. Evidence of long‐range σ‐participation in the stabilization of carbocations
Author(s) -
Chow Tahsin J.
Publication year - 1998
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199812)11:12<871::aid-poc76>3.0.co;2-o
Subject(s) - solvolysis , chemistry , carbocation , delocalized electron , ab initio , computational chemistry , kinetic energy , photochemistry , organic chemistry , hydrolysis , physics , quantum mechanics
Enhanced rates of solvolysis have been reported for some isodrin derivatives, e.g. compounds 2, 3, 6 and 7 compared with anti ‐7‐norbornene ( 1 ). The effect has been ascribed to the formation of laticyclic (2 + 2 + 0) π‐delocalization on a carbocation such as 5 . However, comparable rates of solvolysis were also observed for analogous monoenes 4, 8, 9 and 12, where no adequate explanation has been provided. Molecular modeling at both semiempirical and ab initio levels shows a good correlation between the stabilization energy of the cations and their kinetic data. The enhanced rate of solvolysis for 4, 8, 9 and 12 can be rationalized by strong effects of σ‐bond participation in the transition state. For both series of compounds, the stabilization effect can be effectively transmitted either through space or through bonds. Copyright © 1998 John Wiley & Sons, Ltd.