
TY  - JOUR
A1  - Ginsburg, Jack Leon 
A1  - Darvesh, Katherine Valenta 
A1  - Axworthy, Patricia 
A1  - Langler, Richard Francis 
T1  - An <emph type="2">Ab Initio</emph> Molecular Orbital Study of Sulfur-Substituted Carbanions: Toward an Understanding of Regiochemistry in the Chlorination of Unsymmetrical Sulfides
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1997
VL  - 50
IS  - 6
SP  - 517
EP  - 522
KW  - 
UR  - https://doi.org/10.1071/C96187 
N2  - Moller-Plesset molecular orbital calculations at the 6-31+G(d) level have been completed on substituted dimethyl sulfide-derived carbanions. The results are applied to the prediction of regiochemistry for chlorination of unsymmetrical sulfides. Notwithstanding the need for future improvements, regiochemical predictions based on stabilities of sulfur-substituted carbanions match experimental results better than earlier predictions based on stabilities of sulfur-substituted carbonium ions or sulfur-substituted free radicals. The present results suggest that the mechanism for the elimination step in the Pummerer rearrangement of a chlorosulfonium cation is an E 1cb-like process. 
ER  -

