Titanium(II) Porphyrin Complexes: Versatile One- and Two-Electron Reducing Agents. Reduction of Organic Chlorides, Epoxides, and Sulfoxides
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Abstract
Treatment of the well-defined complexes (TTP)Ti(η2-EtC⋮CEt) or trans-(TTP)Ti(THF)2 with vicinal dichloroalkanes or dichloroalkenes results in the production of alkenes or alkynes and 2 equiv of (TTP)TiCl. This net two-electron redox reaction arises from two formal one-electron reduction processes mediated by chlorine atom transfer. Oxygen atom transfer occurs when the Ti(II) porphyrins are treated with several different sulfoxides or epoxides, resulting in two-electron redox products, (TTP)TiO, the sulfide or alkene, and EtC⋮CEt or THF. The electronic properties of the substituents on the sulfoxides or epoxides correlate with the yield and rate of the deoxygenation reactions.
Comments
Reprinted (adapted) with permission from Journal of Organic Chemistry 63 (1998): 356, doi:10.1021/jo971893p. Copyright 1998 American Chemical Society.