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47.1.4.8.5 Variation 5: From 1,3-Dioxolane- and 1,3-Dithiolane-2-thiones

DOI: 10.1055/sos-SD-047-00322

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V.Science of Synthesis, (201047849.

Cyclic thionocarbonates (1,3-dioxolane-2-thiones) are readily available from vic-1,2-diols by treatment with 1,1-thiocarbonyldiimidazole, thiophosgene, or by other ways, and provide high yields of alkenes upon treatment with phosphorus(III) compounds or other reducing agents. Moreover, this reductive elimination proceeds stereospecifically with retention of the dioxolane configuration in the alkene; therefore, the conversion of a vic-diol into a thionocarbonate, followed by its reduction, can be considered as a versatile and mild two-step method for the stereoselective preparation of alkenes from 1,2-diols. Analogously, cyclic trithiocarbonates (1,3-dithiolane-2-thiones), which can be synthesized from trans-adducts of dithiocyanogen to alkenes or from oxiranes and potassium methyl trithiocarbonate, undergo reductive fragmentation upon treatment with phosphites, butyllithium, or other reductants (see also HoubenWeyl, Vol. 5/1b, p 747) (Scheme 54).[‌203‌,‌244‌,‌245‌]

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