Novel Chemistry of Small-membered Heterocycles Containing Sulfur-Heteroatom Bond

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The followings are new results developed by the present project.1.Thiirane 1-imides (1)were synthesized by reactions of thiiranes (2)carrying sterically congested substituents with Chloramine T at room temperature. Whereas letting solutions of the thiirane 1-imides derived from 2,2'-biadamanrylidene sulfide (2a) and anti-and syn-2'-adamantylidene-9-benxonorbornenylidene sulfides (2b and 2c) stand at room temperature or above or heating neat, the corresponding alkenes and thiiranes were obtained. On the other hand, ring-expansion of the thiirane 1-imides derived from anti, syn-and anti, anti-9,9'-bibenzonorbornenylidene sulfides (2d and 2e) took place with retention of the configuration to give the corresponding 1,2-thiazetidines (3d and 3e).2.S-Aminothiiranium salts (4)were synthesized by reactions of 2a, 2d, and 2e with O-mesytylenesulfonylhydroxylamine at low temperatures. The compounds 4 were labile in solution above 0℃. Whereas 4a and 4d decomposed to the corresponding alkenes (5)a … More nd 2,ring-expansion of 4e proceeded with retention of the configuration to form MH^+-1,2-thiazetinium salt (6e). Reaction of 6e with aqueous NaHCO_3 in CH_2Cl_2 at 0℃ gave N-unsubstituted 1,2-thiazetidine 7e.3.Reaction of thiirane 1-oxide 8d derived from 2d with TMSOTf at room temperature for 8 days gave ketone 9 hi moderate yield according to pinacol-type rearrangement, together with a mixture of 2d and 2e. The reaction of 7e derived from 2e proceeded more slowly than that of 8d to afford 9,2d, and 2e in 5,1, and 4% yields, respectively along with 8e in 90% yield. The thiirane 1-oxide 8f derived from syn, syn-9,9'-bibenzonorbomenylidene sulfide 2f did not react with TMSOTf.4.1,2-Thiazetidine 1-imides (9) were synthesized by reaction of 2'-adamantylidene-9-benzonorbornenylidene (5b) and anti-and syn-9,9'-bibenzonorbornenylidenes (5d and 5e) with an excess amount of N-sulfinyl-p-toluenesulfonamide. The reaction of 2,2'-biadamantylidene (5a) with TsNSO did not take place. Reactions of 9d and 9e with SmI_2 gave the corresponding 1,2-thiazetidines 3d and 3e, whereas that of 9b afforded 2b, 5b, and aziridine 10b.5.Synthetic method of thiirane from alkene was developed. Reaction of 5b with oligothiodimorpholine and Bronsted acid gave a mixture of 2b and 2c. When CF_3CO_2H was used, isomerization from 2c to 2b was observed. Less