Studies on the Active Molecules Prepared by Accumulation and Amplification of the Transannular Interaction between Chalcogen Atoms

硫族原子跨环相互作用累积放大制备活性分子的研究

• 批准号: 07404035
• 负责人: FURUKAWA Naomichi
• 金额: $ 22.27万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07404035/
• 关键词: Transannular Interaction; Dithia Dications; Hypervalent Compounds; 2-Center 2-Electron Bond; 3-Center 4-Electron Bond; Thiasulfonium Salts; S_Nl Reaction; Dealkylation; 脱アルチル化; O,O'-ビフェニルジスルフィド; ジセレニド; 脱カルボニル; 光反応; 渡環相互作用; 高配位化合物; ナフタレンジスルフ

In this studies, it was described the preparation of the dications having 2-center-2-electron [2c-2e] system and highcoordinated dications having 3-center-4-electron [3c-4e] bonds using organic compounds bearing multiple-chalcogen atoms arranged in space. The dications of [2c-2e] substituted by alkyl and benzyl groups at the chalcogen atoms were found to be quite reactive, and their formation was either undetected or detected only by low temperature ^1H-and ^<13>C-nmr spectroscopy. These dications once formed undergo facile dealkylation to afford N-alkyl acetamides which are trapped by CH_3CN used as a solvent together with thia-sulfonium salts in high yields. The mechanism for this dealkylation is rationally explained to proceed via an S_Nl-type substitution mechanism. On the other hand, the photolysis of the monooxides, mono-N-tosylsulfilimines and mono-S-ylides of naphtho [1,8-de] -1,3-dithiin provided the corresponding ketones, N-imines and olefins quantitatively. The photolysis re … More actions may proceed via the activation of the S-S interaction of these compounds. As to the highcoordinated [3c-4e] dication species, 1-phenyl 2,6-dimethylthiomethylphenyl tellurides were converted to the telluranes on oxidation. Similarly, 1,11-methanoseleno- [or-thio] diselenocin (or dithiocin) afforded the corresponding selenurane (or sulfurane) compounds on treatment of the diselenocin (or dithiocin) with one electron oxidant such as NOBF_4. These [3c-4e] hypervalent dications can be converted readily to the starting tris-selenides (or sulfides) by reducing the dications. In these oxidation-reduction reactions of the trisselenides (or sulfides), these compounds show molecular hysteresis during oxidation-reduction. The dications were stable enough to be isolated and their structures were determined by X-ray crystallographic analysis. The ab initio MO-calculation of these compounds reveal the charge-distribution among the atoms in the hypervalent molecules which was discussed with their reactivities. Less

本研究利用多硫族元素的有机化合物，制备了具有2-中心-2-电子[2c-2 e]体系的双配位阳离子和具有3-中心-4-电子[3c-4 e]键的高配位双配位阳离子。发现在硫族元素原子上被烷基和苄基取代的[2c-2 e]二价阳离子具有很强的反应性，它们的形成要么未被检测到，要么只能通过低温^1H-和^C-NMR光谱检测到<13>。这些二价阳离子一旦形成，就容易脱烷基化，得到N-烷基乙酰胺，然后用CH_3CN作溶剂与硫杂锍盐一起捕集，产率很高。对脱烷基反应机理进行了合理的解释，认为脱烷基反应是通过S_N1型取代反应机理进行的。萘并[1，8-de]-1，3-二噻英的单氧化物、单-N-对甲苯磺酰亚胺和单-S-叶立德的光解则定量地生成相应的酮、N-亚胺和烯烃。光解反应 ...更多信息 通过这些化合物的S-S相互作用的活化可以进行作用。对于高配位的[3c-4 e]阳离子，1-苯基-2，6-二甲硫基甲基苯基碲化物在氧化过程中转化为碲烷。类似地，用单电子氧化剂NOBF_4处理1，11-亚甲基硒代- [或-硫代]二硒新（或二硫代），得到相应的硒铀烷（或硫烷）化合物。这些[3c-4 e]高价二价阳离子可以通过还原二价阳离子容易地转化为起始三硒化物（或硫化物）。在三硒化物（或硫化物）的这些氧化还原反应中，这些化合物在氧化还原期间显示分子滞后。该化合物稳定性好，可以分离得到，并通过X-射线晶体学分析确定了它们的结构。对这些化合物的从头算MO-计算揭示了超价分子中原子间的电荷分布，并讨论了它们的反应活性。少

项目成果

Naomichi, Furukawa・et al.: "Mechanism for Photodecomposition of Naphto[1,8-de][1,3]dithiin-l-bis(ethoxycarbonyl)methylides." Tetrachedron Lett.36. 8039-8042 (1995)

Naomichi, Furukawa 等：“Naphto[1,8-de][1,3]dithiin-l-bis(ethoxycarbonyl)methylides 的光分解机制。”Tetrachedron Lett.36 (1995)。

Naomichi Furukawa: "Activation and Facile Dealkylation of Monooxides of 2,2′-Bis (alkylthio) biphenyl with Triflic Anhydride Salts" Tetrahedron Lett.37. 667-670 (1996)

Naomichi Furukawa：“2,2-双（烷硫基）联苯的一氧化物与三氟甲磺酸酐盐的活化和轻松脱烷基化”Tetrahedron Lett.37（1996）。

Naomichi Furukawa: "One-Pot Diels-Alder Reaction of N-p-Tosylsulfilimines Generated by BF_3-Et_2O Catalyzed Transformation of Naphtho[1,8-de]dithiin-1-N-p-Tosylsulfilimines" Tetrahedron Lett.36. 4813-4816 (1995)

Naomichi Furukawa：“BF_3-Et_2O 催化 Naphtho[1,8-de]dithiin-1-N-p-Tosylsulfilimines 转化生成 N-p-Tosylsulfilimines 的一锅 Diels-Alder 反应”Tetrahedron Lett.36。

Naomichi Furukawa et al.: "Isolation and Structure of Bis(2,2'-biphenylylene)dichloro-,and-difluoropertellurane,[12-Te-6(C4X2),X=Cl,F](λ^6-Tellane)" Organometallics. 15. 3256-3258 (1997)

Naomichi Furukawa 等人：“双(2,2-亚联苯基)二氯-和-二氟pertellurane,[12-Te-6(C4X2),X=Cl,F](λ^6-Tellane)的分离和结构“有机金属学。15。3256-3258（1997）

Naomichi Furukawa: "The Pummerer and the Thio-Claisen-type Rearrangements of Naphtho [1,8-bc]-1,5-dithiocin Monooxide and N-p-Tosvlsulfilimine" Heteroatom Chemistry. 6. 559-565 (1995)

Naomichi Furukawa：“Pummerer 和萘并 [1,8-bc]-1,5-二硫辛一氧化物和 N-p-Tosvlsulfilimine 的硫代克莱森型重排”杂原子化学。