Antihydrophobic cosolvent effects detect two different geometries for an S(N)2 displacement and the change to a single-electron-transfer mechanism in related cases

Journal of the American Chemical Society

Volumn 118, Issue 26, 1996, Pages 6323-6324

  Breslow, Ronald ^a   Connors, Richard ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; ETHER DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; ELECTRON TRANSPORT; REACTION ANALYSIS; THEORY;

EID: 0030018858     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960868i     Document Type: Article

References (14)

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3. Using Macromodel (ref 4), we calculated the energy of 2,6-dimethylanisole and of 2,6-dimethylthioanisole as the methyl on oxygen or sulfur was brought through the ring plane by rotation of the phenyl-O (or S) bond. The barrier was larger (5.7 kcal/mol) in the sulfur case than in the oxygen case (1.4 kcal/mol), since the smaller C-S-C angle more than compensated for the longer C-S bond lengths.
4. Still, W. C.; Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Lipton, M.; Liskamp, R.; Chang, G.; Hendrickson, T.; DeGunst, F.; Hasel, W. MacroModel, v 3.5; Department of Chemistry, Columbia University: New York, NY 10027.
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10. Saveant, J.-M. Advances in Physical Organic Chemistry; Bethel, D., Ed.; Academic Press: New York, 1990; Vol. 26, pp 1-130. Saveant, J.-M. Acc. Chem. Res. 1993, 26, 455.
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13. We saw a related effect, in the opposite direction (ref 1), when a Hydrophobic imidazole ring became less hydrophobic as it acquired positive charge.
14. Kornblum, N. Angew. Chem., int. Ed. Engl. 1975, 14, 734.