ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The ab initio SCF-MO method was employed to examine the possibility of a reaction pathway without a carbocation intermediate in the pinacol rearrangement. The molecular geometries of the transition states were obtained for the 1,2-hydride shift together with H2O elimination, starting from the various methyl-substituted protonated 1,2-diols. It was found that the activation energies depend strongly on the substitutents. A comparison of the relative energies between β-hydroxycarbonium ions and the transition states of the concerted mechanism suggests that the stepwise mechanism is less favourable than the concerted path in each case.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610031107
