ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Ab initio calculations were carried out on systems with a geometrically constrained relationship between a double bond and a homoallylic substituent X, as in YC=CCCX. The axial-equatorial equilibria in 3-substituted methylenecyclohexanes and 4-substituted cyclohexenes are determined largely by the homoallylic interaction between X and the double bond. The homoallyic substituent was chosen to be OCH3, and the nature of the double bond was varied by changing Y (H, CH3, F, Cl, CN). NMR experiments previously had found very significant dependences of the axial-equatorial equilibrium on the nature of the X and Y substituents. Electrostatic calculations, based on Mulliken charges, reproduce the experimental (NMR) substituent effects on the axial-equatorial equilibrium and suffice to explain all the observations.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610030710
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