Mechanism and stereochemistry of organic reactions. Organic sulfur chemistry
Tradational Division: Organic
B.Sc., Ph.D., New Brunswick
Merck Frosst Award
The point of our research is to learn more about how reactions take place and to apply the insights so obtained to the development of new methods. We are currently studying (a) reactions of organic sulfur compounds, (b) systems designed to illuminate stereoelectronic effects, and (c) the use of water as a solvent for organic reactions.
Specific topics include:
Organic sulfur reactions. The study of the mechanisms of (a) reactions of sulfonyl compounds with nucleophilic reagents, (b) the chemistry of sulfenes, including possible preparation of a stable sulfene, (c) synthesis of a long chain sulfobetaine.
Stereoelectronic effects. Dependence of ease of formation of alpha-sulfonyl carbanions on the nature and geometry of beta-substituents. The importance of negative hyperconjugation in substituent effects.
Water as a solvent for organic reactions. Water is readily and cheaply available in pure form, it is environmentally friendly, and is the solvent in which the reactions of living matter take place. Why, then, is it not used more in industrial and laboratory synthesis of organic compounds? Our previous work has shown examples of the importance of pH-control in obtaining high yields and selectivity in organic reactions. We propose to continue their study of pH-optimization and to investigate new reactions carried out in water by means of pH-yield studies.
"Experimental Evidence for Negative Hyperconjugation as a Component of the Polar Effect: Variation of the Ease of a-Sulfonyl Carbanion Formation with the Orientation of a b-Alkoxy Substituent", J.F. King, R. Rathore, Z. Guo. M. Li, and N.C. Payne, J. Am. Chem. Soc. 122, 10308-10324 (2000).
"Reversible and Irreversible ElcB Mechanisms in the Hydrolysis of 2,2,2-Trifluoroethanesulfonyl Chloride: Carbanion Intermediates in Aqueous Acid", J.F. King and M.S. Gill, J. Org. Chem. 63, 808-811. (1998)
"Stereoelectronic Effects in Sulfonyl Compounds: Axial Orientation of an N-methyl Group in a Six-Membered Sultam", J.F. King, G. Yuyitung, M.S. Gill, J.C. Stewart and N.C. Payne, Can. J. Chem. 76, 164-170. (1998)
"Alkyl 2,2,2-Trifluoroethanesulfonates (Tresylates): Elimination-addition vs Bimolecular Nucleophilic Substitution in Reactions with Nucleophiles in Aqueous Media", J. F. King and M.S. Gill, J. Org. Chem., 61, 7250-7255 (1996).
"Mechanisms of Reactions of Sulfonyl Compounds with Nucleophiles in Protic Media" J.F. King, M.S. Gill, D.F. Klassen, Pure Appl. Chem. 68, 825-830 (1996).