Journal
JOURNAL OF MOLECULAR STRUCTURE
Volume 1157, Issue -, Pages 149-158Publisher
ELSEVIER
DOI: 10.1016/j.molstruc.2017.12.055
Keywords
Amino alcohols; Rearrangement; Quantum chemical calculations; XRD analysis; 2D NMR investigation
Categories
Funding
- Ministry of Education and Science of Ukraine [0113U003036, 0116U001520]
- National Science Foundation [ACI-1053575]
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Aminolysis of 3,4-epoxysulfolane in aqueous media leads to a very complex mixture of products with unresolved stereochemistry. Herein, we report a detailed theoretical and experimental mechanistic investigation of this reaction along with extensive spectroscopic characterization of the resulting amino alcohols, using 1D and 2D NMR techniques (H-1, C-13, NOE, NOESY, COSY, HSQC, HMBC) as well as XRD analysis. In addition to simple amines such as ammonia and benzylamine, our study also employed the more sterically hindered endo-bicyclo[2.2.1]hept-5-en-2-ylmethanamine. The mechanism of the aminolysis of 3,4-epoxysulfolane by aqueous ammonia was studied in more detail using quantum chemical calculations at the M06-2X/6-31++G** level of theory. The computational results led us to conclude that the most probable way of initial epoxide transformation is base-catalyzed rearrangement to a corresponding allylic alcohol. Subsequent formation of vicinal amino alcohols and diols proceeds via addition of ammonia or hydroxy-anions to activated double C=C bond with some preference of a cis-attack. Detailed analytical data obtained in the course of our work will be useful for the stereochemical identification of new sulfolane derivatives. (C) 2017 Elsevier B.V. All rights reserved.
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