ISSN:
0894-3230
Keywords:
laticyclic hyperconjugation
;
isodrin
;
solvolysis
;
through-bond and through-space interactions
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
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.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
