Issue 13, 2016

Type-I dyotropic rearrangement for 1,2-disubstituted cyclohexanes: substitution effect on activation energy

Abstract

For an array of judiciously selected 1,2-disubstituted cyclohexane motifs, the migratory aptitude and contribution of specific structural features of synthetically valuable functional groups and halogen atoms in type-I dyotropic rearrangement are reported by employing quantum chemical calculations. This double migration process requires higher activation barriers for carbon, silicon and nitrogen bearing substituents, however, it is thermally allowed and a feasible approach for several important moieties including oxygen, sulphur, phosphorous and halogen atoms bearing migrating fragments. Strong positive correlations are observed by plotting representative activation energy trends against inductive sigma (σI), field (σF), steric substituent (Es) and polar substituent (σ*) constants. Also, an effect of the asymmetric combinations of substituents is presented which provides an interesting insight into such substitution patterns.

Graphical abstract: Type-I dyotropic rearrangement for 1,2-disubstituted cyclohexanes: substitution effect on activation energy

Supplementary files

Article information

Article type
Paper
Submitted
01 Dec 2015
Accepted
11 Jan 2016
First published
19 Jan 2016

RSC Adv., 2016,6, 10549-10556

Author version available

Type-I dyotropic rearrangement for 1,2-disubstituted cyclohexanes: substitution effect on activation energy

N. S. Sheikh, RSC Adv., 2016, 6, 10549 DOI: 10.1039/C5RA25482E

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