Direct Synthesis of Thiiranes from Alkenes Using Diaminoligosulfane and Acid Catalyst

使用二氨基低聚硫烷和酸催化剂直接从烯烃合成硫杂丙环

• 批准号: 17550030
• 负责人: SUGIHARA Yoshiaki
• 金额: $ 2.52万
• 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: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17550030/
• 关键词: alkene; thiirane; thiiranation; vulcanization; diaminoligosulfane; Bronsted acid; metal triflate; retention of configuration; チイラン化; 4,4'-ジチオジモルホリン; 4,4'-テトラチオジモルホリン; 1,1'-ジチオビス(1H-1,2,4-トリアゾール); サッカリンジスルフィド; 1.2ベンゾジチオール-3-オン1-オキシド; 1.2-ベンゾジ

The followings are new results developed by the present project. 1. Direct synthesis of thiiranes from alkenes using 4,4'-oligothiodimorpholines in the presence of Bronsted acid or metal triflate was investigated. Thus,2-adamantylidene-9-benzonorbornenylidene 1 reacted with 4,4'-teirathiodimorpholine 2, 4,4'-dithiodimorpboline 3, and 4,4'-thiodimorpholine 4 in the presence of carboxylic acid or ptoluenesulfonic acid to give the corresponding thiiranes. When carboxylic acid was used, the rate of reaction was faster as its pK_a value was smaller. Unfortunately, isomerization and decomposition of the resulting thiirane was observed in most of the reactions. Reactivity of 4,4'-oligothiodimorpholiws toward 1 is found to be 2> 3> 4. 2. The direct synthesis of thiiranes using 4,4'-dithiodimorpholine 3 and arid anhydride was investigated. Although reactions of 1 and 3 with highly reactive acid anhydride such as Tf_2O, TfOAc, Ts_2O, and (CF_3C0)_2O took place to form the corresponding thiiranes in moderate yields, their isomerization and decomposition also occurred. The reaction with excess of Ac_2O proceeded to give the thiiranes without the isomerization and decomposition of the products. 2,2'-Biadamantylidene 5, and trans- and cis-cyclooctene, 6 and 7, also reacted to furnish the corresponding thiiranes under the same conditions. 3. The direct synthesis of thiiranes using N, N-dithiobisazoles was investigated. Although the reaction of 1 with N, N-Dithiobisbenzimidazole 8 in the absence of Cu (Otf)_2 and Sc (Otf)_3 did not occur, that with N,N-dithiobis (1H-1,2,4-triazole) 9 proceeded even at-15℃. The alkenes 5-7, norbornene, and anti- and syn-9,9'-bibenzonorbomenylidenes, 8 and 9 also reacted to furnish the corresponding thiiranes with retention of configuration of the alkenes under the same conditions.

以下是本项目取得的新成果。1.研究了在Bronsted酸或金属三氟化钠存在下，4，4‘-低聚硫二吗啉催化烯烃直接合成硫杂环己烷的反应。因此，在羧酸或对甲苯磺酸存在下，2-金刚烷-9-苯甲醛-1与4，4‘-硫代二吗啉2，4，4’-二硫代二吗啉3和4，4‘-硫代二吗啉4反应生成相应的硫杂环。当使用羧酸时，反应速度较快，pK_a值较小。不幸的是，在大多数反应中都观察到了生成的硫杂环己烷的异构化和分解。4，4‘-低聚硫二吗啉与1的反应活性为2&gt；3&gt；4.2。研究了4，4’-二硫代二吗啉3与脱水酸酐直接合成硫杂环己烷的反应。1和3与高活性酸酐如Tf_2O、TfOAc、TS_2O和(Cf_3C0)_2O反应生成相应的硫杂环，产率适中，但它们也发生了异构化和分解。过量的Ac_2O继续反应生成硫杂环，而不发生异构化和分解。在相同条件下，2，2‘-联金刚烷5和反式和顺式环辛烯6和7也反应生成相应的硫杂环。3.研究了N，N-二硫代二氮唑直接合成硫杂环己烷的反应条件。尽管在没有铜(OTf)_2和Sc(OTf)_3的情况下，1与N，N-二硫双苯并咪唑8没有发生反应，但即使在-15℃时，与N，N-二硫双(1H-1，2，4-三唑)9的反应仍在进行。在相同的条件下，5-7烯烃、降冰片烯、反式和合成-9，9‘-联苯并苯亚甲基、8和9也反应生成相应的硫杂环并保持其构型不变。

项目成果

Direct Synthesis of Thiirane from Alkene Using 4, 4'-Dithiodimorpholine and Acid Anhydride

使用 4, 4-二硫代二吗啉和酸酐从烯烃直接合成硫杂丙环

• 发表时间: 2007
• 作者: 新正裕尚;折橋裕二;(他3名);奥田 晴紀;Harunori Okuda;Masatoshi Arai;Hiroki Koyama
• 通讯作者: Hiroki Koyama

Synthesis and Properties of Novel Thiirane 1-Imides and S-Aminothiiranium Salts

新型硫杂环丙烷1-酰亚胺和S-氨基硫杂环丙烷盐的合成与性能

• 发表时间: 2005
• 作者: 新正裕尚;折橋裕二;(他3名);奥田 晴紀;Harunori Okuda;Masatoshi Arai;Hiroki Koyama;Sanae Yoshida;野積 宏子;吉田 佐奈枝;Hiroko Nozumi;Sanae Yoshida;奥田 晴紀;吉田 佐奈枝;野積 宏子;Harunori Okuda;Sanae Yoshida;Hiroko Nozumi;野積 宏子;Hiroko Nozumi;杉原 儀昭;Yoshiaki Sugihara
• 通讯作者: Yoshiaki Sugihara

Ring-enlargement of Thiiranes Using PhNCO and Lewis Acid

使用 PhNCO 和路易斯酸扩环硫杂丙环

• 发表时间: 2008
• 作者: 新正裕尚;折橋裕二;(他3名);奥田 晴紀;Harunori Okuda
• 通讯作者: Harunori Okuda

Synthesis of Diazines by Sulfuration of 1, 2-Diamines

1, 2-二胺硫化合成二嗪

• 发表时间: 2006
• 作者: 新正裕尚;折橋裕二;(他3名);奥田 晴紀;Harunori Okuda;Masatoshi Arai;Hiroki Koyama;Sanae Yoshida;野積 宏子;吉田 佐奈枝;Hiroko Nozumi;Sanae Yoshida;奥田 晴紀;吉田 佐奈枝;野積 宏子;Harunori Okuda;Sanae Yoshida
• 通讯作者: Sanae Yoshida

Direct Synthesis of Thiirane from Alkene Using 4, 4'-Ologothiodimorpholines and Metal Triflate

使用 4, 4-低硫二吗啉和金属三氟甲磺酸盐直接从烯烃合成硫杂丙环

• 发表时间: 2006
• 作者: 新正裕尚;折橋裕二;(他3名);奥田 晴紀;Harunori Okuda;Masatoshi Arai;Hiroki Koyama;Sanae Yoshida;野積 宏子;吉田 佐奈枝;Hiroko Nozumi;Sanae Yoshida;奥田 晴紀;吉田 佐奈枝;野積 宏子;Harunori Okuda;Sanae Yoshida;Hiroko Nozumi
• 通讯作者: Hiroko Nozumi