Reactivity Pattern of Bis(propargyloxy) Disulfides: Tandem Rearrangements and Cyclizations

Abstract

Thirty-five substituted bis(propargyloxy) disulfides were successfully prepared in good to excellent yields, and their reactivity was found to be strongly dependent on the substitution pattern of the reactant. Inter alia they undergo surprising tandem sigmatropic rearrangements and cycloadditions. Three heretofore unknown product types were isolated and fully characterized: 6,7-dithiabicyclo[3.1.1]heptan-2-one 6-oxide derivatives, two isomeric 1,2-dithiete 1,1-dioxides (α,β-unsaturated four-membered cyclic thiosulfonates) from bis(propargyloxy) disulfides with α- or γ-alkyl-substituted propargyl groups, and two isomeric 2-oxa-5,7-dithiabicyclo[2.2.1]heptane 5-oxides from bis(propargyloxy) disulfides with α-tert-butyl- or α,α-dialkyl-substituted propargyl groups.

Key words

sigmatropic rearrangements - cycloadditions - substituent effects - bis(propargyloxy) disulfides - dithiabicyclic structures - organosulfur chemistry - thiosulfonates - vic-disulfoxides

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9

Bis(propargyloxy) disulfide 9d did not undergo rearrangement. No rationale is proposed. After six hours in chloroform solution at room temperature, the compound decomposed to the corresponding propargylic alcohol 2d.

12

The stereochemistry of the two double bonds in these structures was established by NOESY experiments, which showed a strong interaction of the respective bridgehead hydrogen atoms with the nearby tert-butyl hydrogen atoms, but no interaction with the vinyl hydrogen atoms.

14

In the case of 9b, this reaction was repeated in anhydrous chloroform (dried over basic alumina) and found to be identical to the present one.