Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 125, Issue 31, Pages 9329-9342Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja035729x
Keywords
-
Categories
Ask authors/readers for more resources
The effects of aromatic stabilization on the rates of [1,5]-hydrogen shifts in a series of carbo-and heterocyclic dihydroaromatic compounds were estimated by B3LYP/6-31G** computations. The aromatic stabilization energy of the product is directly translated into increased exothermicity of these reactions. Relative trends for a significant range of endothermic and exothermic [1,5]-shifts with different intrinsic activation energies are reliably described by Marcus theory. The effects of aromaticity or antiaromaticity are very large and can lead to dramatic acceleration or deceleration of [1,5]-hydrogen shifts and even to complete disappearance of the reaction barrier. Not only the activation energy but the shape and position of the reaction barrier can be efficiently controlled by changes in the aromaticity of the products, making these systems interesting models for studying hydrogen tunneling. Marcus theory can also be applied successfully to other pericyclic shifts such as [1,5]-shifts which involve chlorine and methyl transfer.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available