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

2004 Fiscal Year Final Research Report Summary

• Project/Area Number: 15550026
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Saitama University
• Principal Investigator: SUGIHARA Yoshiaki Saitama University, Faculty of Science, Department of Chemistry, Associate Professor, 理学部, 助教授 (00272279)
• Co-Investigator(Kenkyū-buntansha): NAKAYAMA Juzo Saitama University, Faculty of Faculty of Science, Faculty of Science, Department of Chemistry, Full Professor, 理学部, 教授 (90092022)
• Project Period (FY): 2003 – 2004
• Keywords: Thiirane 1-imides / 1,2-Thiazetidines / S-Aminothiiranium salts / NH^+-1,2-thiazetidinium salt / Thiirane 1-oxides / Pinacol-type rearrangement / 1.2-Thiazetidine 1-imides / Thiiranation

Research Abstract

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 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.