Type-I dyotropic rearrangement for 1, 2-disubstituted cyclohexanes: substitution effect on activation energy. Issue 13 (26th January 2016)

• Record Type: Journal Article
• Authors: Sheikh, Nadeem S.
• Is Part Of: RSC advances. Volume 6:Issue 13(2016)
• Page Start: 10549
• Page End: 10556
• Publication Date: 2016-01-26
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c5ra25482e
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Migratory aptitude and contribution of specific structural features of synthetically valuable functional groups and halogen atoms in type-I dyotropic rearrangement for both symmetric and unsymmetrical 1, 2-disubstituted cyclohexanes are computed. 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 ( σ I ), field ( σ F ), steric substituent ( E s ) 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.