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2,7-Di-tert-butylnaphtho[1,8-cd][1,2]dithiole 1,2-dioxides: thermally stable, photochemically activevic-disulfoxides

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Grainger, Richard S., Patel, Bhaven and Kariuki, Benson M. (2009) 2,7-Di-tert-butylnaphtho[1,8-cd][1,2]dithiole 1,2-dioxides: thermally stable, photochemically activevic-disulfoxides. Angewandte Chemie International Edition, 48 (26). pp. 4832-4835. ISSN 1433-7851

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Abstract

Oxidation and reduction of the disulfide (SS) bond are fundamental transformations of importance not only in chemistry, but also in many biological systems (e.g. proteins containing SS bridges) and in materials science (e.g. in the vulcanization of rubber). vic-Disulfoxides (a-disulfoxides) are reactive intermediates in the electrophilic oxidation of thiosulfinates to thiosulfonates (Scheme 1).[1] Compared with acyclic vic-disulfoxides,[2] cyclic variants show greater stability. Folkins and Harpp were able to identify vic-disulfoxides of type 1 that persist above 08C in solution.[3] More recently, Nakayama, Ishii, and co-workers succeeded in isolating vicsulfoxides 2–7 in the solid state.[4–7] However vic-disulfoxides 2–7 still undergo further reaction in solution at room temperature or below. Herein, we report two novel diastereomeric vic-disulfoxides that have a significantly higher barrier to thermal rearrangement than 1–7. Also, the first example of a photomediated epimerization reaction for this bonding motif is reported.

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