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

以下是本项目取得的新成果。以硫烷(2)为载体，在室温下与氯胺T反应合成了硫烷1-亚胺(1)。将2,2′-双金刚烷酰亚胺硫化物（2a）和反-2′-金刚烷酰亚胺-9-苯甲二硼酰亚胺硫化物（2b和2c）的溶液置于室温或更高温度下加热，可得到相应的烯烃和硫烷。另一方面，由反、正、反、反9,9′-双苯并甲氧基苯乙烯硫化物（2d和2e）衍生出的1-噻唑烷酰亚胺发生扩环反应，构型保持不变，得到相应的1,2-噻唑苷（3d和3e）.2。采用2a、2d和2e与o -甲基亚磺酰羟胺在低温下反应合成了s -氨基硫铵盐(4)。化合物4在0℃以上的溶液中不稳定。而4a和4d分解成相应的烯烃(5)a…More和2,4e的扩环继续保持构型形成MH^+-1,2-噻嗪盐（6e）。6e与NaHCO_3水溶液在CH_2Cl_2中于0℃反应得到n -未取代1,2-噻唑替丁7e。由2d衍生的1-氧化物硫代烷8d与TMSOTf在室温下反应8d，与2d和2e的混合物一起，根据pinacol型重排得到酮9高产中。由2e得到的7e的反应速度比8d慢，分别以5%、1%和4%的产率得到9、2d和2e，而8e的产率为90%。的thiirane 1-oxide 8 f源自syn syn-9, 9 ' -bibenzonorbomenylidene硫化2 f与TMSOTf.4.1没有反应,2-Thiazetidine 1-imides(9)被反应合成2》-adamantylidene-9-benzonorbornenylidene (5 b)和反以色列syn-9, 9 ' -bibenzonorbornenylidenes (5 d和5 e)与过量N-sulfinyl-p-toluenesulfonamide。2,2'-双金刚烷二烯（5a）与TsNSO未发生反应。9d和9e与SmI_2反应得到相应的1,2-噻唑烷3d和3e， 9b反应得到相应的2b、5b和叠氮啶10b.5。研究了由烯烃合成硫代烷的方法。5b与低硫碘二morpholine和Bronsted酸反应得到2b和2c的混合物。当使用CF_3CO_2H时，观察到2c到2b的异构化。少

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