Theoretical studies on the cyclization process of a new organosulfur reaction

• Published in: Journal of molecular structure. Theochem 1995-01, Vol.331 (1), p.187-194
• Main Authors: Zhu, Jin, Yan, Da-Yu, Chen, Ya-Ling, Zeng, Guang-Fu
• Format: Article
• Language: English
• ISSN: 0166-1280; 1872-7999
• DOI: 10.1016/0166-1280(94)03789-N

The cyclization process of a new organosulfur reaction was studied by the MNDO (UHF) method. The first reaction path was assumed to be via the organosulfur radical intermediate, the second via the ionic (cationic and anionic) intermediates. The dehydroxylation process was assumed to occur with the synergistic cyclization. The results obtained indicate that the potential energy barrier of the first reaction path was about 102 kcal mol −1, and although the formation of the ionic intermediate is comparatively difficult, the potential energy barrier of the second path is comparable to the first. The sequential reaction path via the radical intermediate, i.e. first cyclization, then dehydroxylation, was investigated for comparison. The cyclization reaction was found to be the thermodynamically favored process, while the ensuing dehydroxylation process was found to have a potential energy barrier of about 62 kcal mol −1.