Design, Synthesis, and Conformational Analysis of Compounds Tailored for the Study of Sulfur-Centered Reactive Intermediates
Neighboring group participation in the oxidation of thioethers provides anchimeric assistance, renders the oxidation potential of thioethers less positive, and stabilizes novelly-bonded reactive intermediates. The nature of the neighboring group has been varied and the participating atom has been nitrogen, oxygen, or sulfur. The effect of the size of the ring formed on participation has been ascertained and formation of five-membered rings is preferable to six-membered rings which, in turn, are favored over other sized rings, in general. Additional geometric constraints have been built into the thioethers studied. Two additional constrained systems that have yielded especially interesting results on oxidation are 2-endo-substituted-6-endo-methylthiobicyclo[2.2.1]heptanes and medium-sized ring thioethers. This review will survey design features in such systems and the synthesis and conformations of such compounds. As will be elaborated upon in this review S-S lone pair-lone pair interactions will also be highlighted.
KeywordsSulfur Atom High Occupied Molecular Orbital Naphthalene Ring Lone Pair Orbital Neighbor Group Participation
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