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

含硫杂原子键小元杂环的新化学

• 批准号: 15550026
• 负责人: SUGIHARA Yoshiaki
• 金额: $ 2.43万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550026/
• 关键词: 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; 1,2-チアゼチジン1-イミド; N-スルフィニルアミド; [2+2]環化付加; 1,2-オイサチエタン; Lewis酸 /

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

本课题取得了以下新的研究成果：1.室温下，由带有空间拥挤取代基的硫杂环丙烷（2）与氯胺T反应，合成了硫杂环丙烷1-酰亚胺（1）。然而，将衍生自2，2 ′-双金刚烷亚基硫化物（2a）和反式和顺式-2 ′-金刚烷亚基-9-苯并降冰片烯亚基硫化物（2b和2c）的硫杂环丙烷1-酰亚胺的溶液在室温或更高温度下静置或加热，得到相应的烯烃和硫杂环丙烷。另一方面，由反式、顺式和反式、反式9，9 ′-二苯并降冰片烯亚基硫醚衍生的硫杂环丙烷1-酰亚胺（2d和2 e）在保持构型的情况下发生扩环反应，得到相应的1，2-硫杂环丁烷（3d和3e）。化合物4在0℃以上的溶液中不稳定。而4a和4d则分解为相应的烯烃（5）a ...更多信息 4 e在保留构型的情况下继续扩环，形成MH^+-1，2-噻氮杂环丁烷鎓盐（6 e）。6 e与NaHCO_3水溶液在CH_2Cl_2中于0℃反应得到N-未取代的1，2-硫氮杂环丁烷7 e。3.由2d衍生的硫杂环丙烷1-氧化物8d与TMSOTf在室温下反应8天得到中等产率的酮9（根据频哪醇型重排）以及2d和2 e的混合物。衍生自2 e的7 e的反应比8 d的反应进行得更慢，分别以5、1和4%的产率得到9、2d和2 e，沿着以90%的产率得到8 e。衍生自顺，顺-9，9 '-二苯并降冰片亚甲基硫醚2f的硫杂环丙烷1-氧化物8 f不与TMSOTf反应。4.1，2-硫氮杂环丁烷1-酰亚胺（9）是通过2'-金刚烷亚基-9-苯并降冰片亚甲基（5 b）与反式和顺-9，9 '-二苯并降冰片亚甲基（5d和5e）与过量的N-亚磺酰基-对甲苯磺酰胺反应合成的。2，2 '-联金刚烷亚基（5a）与TsNSO没有发生反应。9d和9 e分别与SmI_2反应生成相应的1，2-硫氮杂环丁烷3d和3e，9 b分别与SmI_2反应生成相应的1，2-硫氮杂环丁烷2b、5 b和氮杂环丙烷10 b。5 b与低聚硫代二吗啉和布朗斯台德酸反应，得到2b和2c的混合物。当使用CF_3CO_2H时，观察到从2c到2b的异构化。少