Reactive and Unusual Molecules

反应性和异常分子

• 批准号: 05303003
• 负责人: ANDO Wataru
• 金额: $ 7.17万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05303003/
• 关键词: silylene; fullerene; reactive intermediate; unusual reactions; strained compounds; perooxysulfinate; long triplet carbene; フラーレン; 歪化合物; 反応性ケイ素種; 活性分子; 異常原子価; 高歪み化合物; 活性種; 反芳香族性; π-共役; 歪み化合物; 活性中間体; ヘテロ原子; 機能性有機材料; 反応制御

Ando has synthesized 9,10-dimethyl-9,10-disilanthracene dimer by treatment of the corresponding dihydrodisilaanthracene with lithium. The dianion is regarded as synthetic equivalent for disilaaromatics with respect to its reactivity toward diphenylacetylene. Tomioka obtained extremely long lived triplet carbene. Oku has reported the ring-expansion reaction via ethereal bicyclooxonium ylides of carbenes.a stable triple carbene. Kira found unique reactions of tetrakis (trialkylsily) disilene and digermenes. Sugimori shows the cyclopentadienyliodo (dimethyldithiocarbamato) cobalt reacts with diazomethane to give a novel complex having a five membered dithiolene ring and four membered cobaltathiethane ring. Sekiguchi reported unique properties of the polyorganosilyllithium. Iyoda reported the unusual reactivities of fullereols and fullerene dimers containing perfluoroalkyl groups. Oda reported the regioselective lithiations carbanion formation of arylmethanes directing towards new synthetic building blocks. Tokitoh have synthesized extremely hindered disilenes bearing a new steric protection group and found the both cis and trans were kinetically very stable but thermally labile to give the corresponding silylene under very mild conditions. Sawaki found the new structure and reactivity of XOO active oxygen species.

安藤用锂处理相应的二氢二蒽，合成了9,10-二甲基-9,10-二蒽二聚体。就其对二苯基乙炔的反应性而言，戊离子被认为是合成的二苯芳烃的等价物。富冈获得了寿命极长的三联体碳。Oku已经报道了通过羰基醚双环氯鎓化物进行的扩环反应。一个稳定的三重碳。基拉发现了四烷基二烯和二烯的独特反应。杉森表示，环戊二烯钴（二甲基二硫代氨基甲酸酯）与重氮甲烷反应生成具有五元二硫代环和四元钴硫代烷环的新型配合物。Sekiguchi报道了多有机硅锂的独特性质。Iyoda报告了含全氟烷基的富勒醇和富勒烯二聚体的异常反应性。Oda报道了芳基甲烷的区域选择性锂化碳离子形成，这些锂化碳离子形成了新的合成构件。Tokitoh合成了具有新的位阻保护基团的极受阻二烯，发现顺式和反式在动力学上非常稳定，但在非常温和的条件下产生相应的硅烯是热不稳定的。Sawaki发现了XOO活性氧的新结构和反应性。

项目成果

M. Nanji, C. Kabuto, H. Sakurai, A. Sekiguchi: "Preparation of (Pentamethyldisilany) lithium and Two Isomers of (Heptamijethyltrisilanyl) lithium. Structural Characterrization of (Ch_3)_5Si_2I_1i'" Organometallics. 14. 2630-2632 (1995)

M. Nanji、C. Kabuto、H. Sakurai、A. Sekiguchi：“（五甲基二硅烷基）锂和（七甲基乙基三硅烷基）锂的两种异构体的制备。(Ch_3)_5Si_2I_1i 的结构表征”有机金属。

T.Natsumot, R.Okazaki, N.Tokitoh: "Formation and reactions of the First Diarylgermanone Stable in Solution" Chemistry Lett.1087-1088 (1995)

T.Natsumot、R.Okazaki、N.Tokitoh：“溶液中第一个稳定的二芳基锗酮的形成和反应”Chemistry Lett.1087-1088 (1995)

T. Kimura, H. Nakayama, N. Furukawa: "Highly Diastereoselective Oxidation of 1-Alkylsulfinyl-9-(Alkylthio) dibenzothiophene with MCPBA in the presence of Trifluoroboran Etherate" Heterocycles. 42. 71-74 (1996)

T. Kimura、H. Nakayama、N. Furukawa：“在三氟硼烷乙醚存在下，用 MCPBA 对 1-烷基亚磺酰基-9-（烷硫基）二苯并噻吩进行高度非对映选择性氧化”杂环。

Y. Matano, M. Yoshimune, H. Suzuki: "Electrophilic Allylation of Arenes with in situ Generated Allyltriarylbismunium Compounds : The Bismuth-Mediated Polarity Inversion of Allylsilane" Tetrahedron lett.36. 7475-7478 (1995)

Y. Matano、M. Yoshimune、H. Suzuki：“原位生成的烯丙基三芳基铋化合物对芳烃进行亲电烯丙基化：铋介导的烯丙基硅烷极性反转”Tetrahedron lett.36。

L. Zhang, C. Kabuto, H. Sakurai, M. Kira: "Synthesis and Structure of Hexacoordinate Organosilicon Compounds Having Tropolonato Ligands" Chemistry Lett.659-660 (1995)

L.Zhang、C.Kabuto、H.Sakurai、M.Kira：“具有 Tropolonato 配体的六配位有机硅化合物的合成和结构”Chemistry Lett.659-660 (1995)