ABOUT THE PARTICIPATION OF SIGMA-ORBITAL, PI-ORBITAL AND N-ORBITAL INTHE SOLVOLYSIS OF 2-OXO-1-NORBORNYL AND 3-OXO-1-NORBORNYL TRIFLATES

Authors
MARTINEZ AG BARCINA JO VILAR ET
Citation
Ag. Martinez et al., ABOUT THE PARTICIPATION OF SIGMA-ORBITAL, PI-ORBITAL AND N-ORBITAL INTHE SOLVOLYSIS OF 2-OXO-1-NORBORNYL AND 3-OXO-1-NORBORNYL TRIFLATES, Tetrahedron, 52(44), 1996, pp. 14041-14048
Citations number
22
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Tetrahedron → ACNP
ISSN journal
00404020
Volume
52
Issue
44
Year of publication
1996
Pages
14041 - 14048
Database
ISI
SICI code
0040-4020(1996)52:44<14041:ATPOSP>2.0.ZU;2-M
Abstract
The solvolysis of 3,3-dimethyl-2-oxo- and 2,2-dimethyl-3-oxo-1-norborn yl triflates (6 and 8) takes place with formation of ring contracted a nd fragmented products respectively. The effect of the substituents on the solvolysis rates is explained taking into account n- and sigma-pa rticipation. This n, sigma-participation causes changes in the structu re and stability of the intermediate carbocations, which can be detect ed by the AM1 method. Copyright (C) 1996 Elsevier Science Ltd.