1H NMR-based kinetic and theoretical studies of the simultaneous formation of two discrete rotameric systems of a novel difenchyl sulfite ester. Issue 49 (7th December 2017)

• Record Type: Journal Article
• Authors: Singh, Alicia; Kaye, Perry T.; Lobb, Kevin A.
• Is Part Of: Tetrahedron. Volume 73:Issue 49(2017)
• Page Start: 6922
• Page End: 6931
• Publication Date: 2017-12-07
• Subjects: Sulfite ester -- Conformational analysis -- Kinetics -- Rotameric equilibria; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tet.2017.10.059
• Languages: English
• ISSNs: 0040-4020

Abstract

Abstract: Attempted repetition of a reported synthesis of fenchene from fenchol has afforded, in high overall yield, a mixture shown by spectroscopic and elemental analysis to comprise a pair of discrete rotameric systems of a novel 2- endo -2′- endo -difenchyl sulfite ester. The kinetics of the formation of these dimeric rotameric systems (I andII ) has been explored experimentally, using 1 H NMR spectroscopic analysis, and theoretically at molecular and quantum mechanical levels. Construction of a theoretical model has permitted calculation of rate constants for each of the steps, while modelling of the transition state complexes corresponding to the rate-determining steps for the formation of the rotameric systemsI andII has revealed their independent access to further sets of interconverting rotamers. Graphical abstract: