Science of Synthesis

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V., Science of Synthesis, (2010) 47, 849.

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 Houben–Weyl, Vol. 5/1b, p 747) (‌Scheme 54‌).[‌203‌,‌244‌,‌245‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeee ee Meeeeeeee Meeeeeeeeee eeee 8,8-Meeeeeeee- eee 8,8-Meeeeeeeee-8-eeeeeee[‌888‌,‌888‌,‌888‌]

Mee eeeeeeeee eeeeeeeeeeeee ee 8,8-eeeeeeeee-8-eeeeeee eeee eeeeeeeee eeee eeeeeeeeee ee eeeee ee eee Meeee–Meeeee eeeeeeeeee.[‌888‌] Mee eeeeeeeeee ee eeee eeeee ee eeeeeeeee eee eeeee eeeeee eee eeeeeeeeeee eeee eeee eeeeeeeee.[‌888‌] Meeeeeeee eeeeeeeeee eeeeeeee eeeeee eee eee eeee eeeeeeeee, eeeeeeee eeee eeeee eeeeeeeeeeee, eeee ee eee(eeeeeeeeeeeeee)eeeeee(8), eeeeeeeeeeeeeeeee(8), ee eeeeeeeeeee eeeeeeee ee eeee eeee ee eee eeee ee 8,8-eeeeeeeee-8-eeeeeee eee eeeeeeeeeeee eee 8,8-eeeeeeeeee-8-eeeeeee, eeee eeee eeeeeee. Mee eeeeeeeee eeee eeeeeeeeee eeeeeeee ee >888°M, eeeeeee eee eee ee eeee eeeeeeeeee eeeeee eeee ee eeeeeeeeeeeeeeeeeeee eeeeeeee eee eeeeeeeeee 8,8,8-eeeeeeeeeeeeeeeeeee eee eeeeeeeee ee 88–88°M. Mee eeeeeeeeeeeeeeee eeeeeee eeeee eeeeeeeeeeee eeeeee eeee eee eeeeeeeeeeeeeeeee. Mee Meeee–Meeeee eeeeeeeeee ee eeeeeeee eee eee eeeeeeeeeee ee eeeeee eeeeeeeeeeeeee ee eeeeeeee eeeeeee, ee eeee ee eee eee eeeeeeeee ee eeeeee eeeeeeeeeeeee.[‌888‌,‌888‌] Mee eeee eeeeeee, eeee eeeeeeee eeee eeee eeeeeeee[‌888‌,‌888‌,‌888‌] (eee eeee Meeeee–Meee, Mee. 8/8e, e 888), eee eeee ee eee eeee eeeeee eeeeeeeee (eeeeeeeee ‌888‌ eeee ‌888‌) eee eeeeeeee ee ‌Meeee 88‌.[‌888‌,‌888‌–‌888‌]

‌Meeee 88‌ Meeeeeeee ee Meeeeee eeee 8,8-Meeeeeeee-8-eeeeeee[‌888‌,‌888‌–‌888‌]

Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeee	Meeee (%)	Mee
	MeM, eeee, 8 e, eeee Me, MeMM, eeeeeeeeee, ee, 8 e		88	[‌888‌]
	8,8-eeeeeeee-8-eeeeee-8,8,8-eeeeeeeeeeeeeeeeee, ee, eeeeeeeee		88e	[‌888‌]
	8,8-eeeeeeee-8-eeeeee-8,8,8-eeeeeeeeeeeeeeeeee, 88°M, 8.8 e, eeee ee, eeeeeeeee		88	[‌888‌]
	MeM, 8,8-eeeeeeeeeeeeee, eeee, 88 e, eeee MeMe, MMM, 8°M, 88 eee		88	[‌888‌]
	M(MMe)8, 888°M, 88 e		88	[‌888‌]

e Mee eee eeeee eeee eeee.

Meeeeeeeeeee Meeeeeeee

Meeeeeee[8.8.8.88,8]eeeeee-8,88-eeeee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeeeeee ee eee eeeeeeeeeeeeeee ‌888‌ (88 ee, 8.88 eeee) ee 8,8-eeeeeeee-8-eeeeee-8,8,8-eeeeeeeeeeeeeeeeee (8.8 eM, 8.8 eeee) eee eeeeeee ee 88°M eee 8.8 e eeeee ee eeeee eeeeeeeeee eee eeee ee eeeee ee ee eeeeeeeee. Mee eeeeeeeeeee eeeeeee eee eeeeeee eeee eeeeeee (8 eM), eeeeeeee ee eeeeee eee, eee eeeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee) ee eeee eee eeeee ee e eeeeeeeee eeeee; eeeee: 88 ee (88%); ee 88.8–88.8°M; 8M MMM (MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8e, 888.