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Dependence of Stereoelectronic and Charge Effects on p K a Values of 1,3‐Dithiane‐Derived Sulfides, Sulfoxides, and Sulfones: An Experimental and Computational Investigation
Author(s) -
Süveges Bastian D.,
Podlech Joachim
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201403409
Subject(s) - chemistry , sulfoxide , deprotonation , proton , computational chemistry , charge (physics) , stereochemistry , medicinal chemistry , organic chemistry , ion , physics , quantum mechanics
The p K a values of conformationally fixed 1,3‐dithianes were investigated with experimental and theoretical methods to gain an insight into the influence of the relative orientation of the acidic proton and the stabilising S=O or S–C bonds. Experimental values were determined with a modification of the spectrophotometric method using overlapping indicators developed by Bordwell; theoretical values were obtained with the proton exchange methods using DFT calculations. It turned out that stereoelectronic stabilisation is important for sulfides and sulfoxides, whereas charge effects become dominant in sulfones. Deprotonation of the equatorial proton is favoured for most of the compounds except for the equatorial/axial bis‐sulfoxide.