Chemical Behaviors and Synthetic Applications of Hypovalent Organic Metastable Species Under WellーControlled Conditions

良好控制条件下低价有机亚稳物质的化学行为及合成应用

• 批准号: 01300011
• 负责人: TAKAYA Hidemasa
• 金额: $ 6.59万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01300011/
• 关键词: metal-carbene complex; carbene; silylene; qermylene; arylcarbene; MO calculation; alkylfluorocarbenoid; allylcarbene-Pt; 二原子価欠損型反応活性種; フィッシャ-型カルベン; 有機強磁性体; 有機磁性体; メタセシス

Researches on syntheses and reactivities of metal-carbene complexes have been carried out extensively. Reactivities of Ni-Carbene complexes generated from nickellacyclobutane toward various substituted olefins have been investigated. New allylcarbene-Pt complexes have been generated by the reaction of Pt (II) complexes and bicyclo [1.1.0] butanes and showed that these complexes are important intermediates in the intra- and intermolecular reaction of bicyclo [1.1.0] butanes catalyzed by transition metals. A family of titanoxycarbene-metal carbonyl complexes has been prepared by the treatment of titanocene-ethylene complex with metal carbonyls of group 6 and 7, and structure-reactivity relationship of these complexes has been elucidated.New methodologies for the generation of carbenes, silylenes, and germylenes have been widely studied and these reactive species have been utilized for organic syntheses. Preparation and reaction of lithium 1-halocyclopropylzincates which are generated fro … More m 1, 1-dibromocyclopropanes were studied. Stereoselective synthesis of gem-disubstituted cyclopropanes was realized by utilizing the above reagent. The catalytic decomposition of alkyl O- (diazoacety) benzoates in the presence of CS_2 was studied and unique 2 : 1-adducts were obtained. alpha, alpha-Chlorofluoroalkyl sulfoxides undergo nucleophilic desulfinylation with a Grignard reagent to give alkylfluorocarbenoids which collapse into cis-fluoroalkenes in the presence of copper (I) iodide. Digermiranes or azadegermiridines were produced from the reaction of digermene with diazomethane or^- phenyl azide. Molecular structures and reactivities of these compounds were also investigated.Several new interesting properties of arylcarbenes have been discovered by the photochemical decomposition of diazo compounds. The reaction modes of diphenylcarbenes bearing methoxy substituents at ortho position are shown to be very sensitive to the meta-alkyl groups which buttress the methoxy group to hang over he carbenic center. Effect of the conformations of the arylcarbenes on the reactivity was shown by the photolysis of rotameric 9- (2-diazomethyl-1-naphthyl) fluorenes.Theoretical studies on the reactions of carbenes have also been done. Addition of singlet carbenes to olefins and effects of substituents on this type of reaction were studied by means of MO calculation. Less

金属-卡宾配合物的合成及其反应性的研究已得到广泛的开展。研究了镍环丁烷生成的镍卡宾配合物对各种取代烯烃的反应性。通过Pt（II）配合物与双环[1.1.0]丁烷的反应，合成了一系列新的烯丙基卡宾-Pt配合物，表明这些配合物是过渡金属催化双环[1.1.0]丁烷分子内和分子间反应的重要中间体.用第6族和第7族金属羰基化合物处理茂钛-乙烯络合物，制备了一类钛氧卡宾-金属羰基络合物，并阐明了这些络合物的结构-反应性关系，研究了生成卡宾、甲硅烯和甲锗烯的新方法，这些反应性物种已被广泛用于有机合成。1-卤代环丙基锌酸锂的制备和反应 ...更多信息 对1，1-二溴环丙烷进行了研究。利用该试剂实现了偕二取代环丙烷的立体选择性合成。研究了CS_2存在下O-（重氮乙酰基）苯甲酸烷基酯的催化分解，得到了独特的2：1加成物。α，α-氯氟烷基亚砜与格氏试剂进行亲核双酰化反应，得到烷基氟卡宾，其在碘化亚铜（I）存在下分解成顺式氟代烯烃。由二锗烯与重氮甲烷或对-苯基叠氮反应产生二锗烷或氮杂锗烷。研究了这些化合物的分子结构和反应活性，并通过重氮化合物的光化学分解发现了芳基卡宾的一些新的有趣性质。邻位带有甲氧基取代基的二苯基卡宾的反应模式对支撑甲氧基悬挂在卡宾中心的间位烷基非常敏感。通过对9-（2-重氮甲基-1-萘基）芴的光解反应研究，揭示了芳基卡宾的构象对反应活性的影响，并对卡宾的反应进行了理论研究。用分子轨道计算方法研究了单重态卡宾与烯烃的加成反应及取代基对这类反应的影响。少

项目成果

Y. Takeyama, K. Oshima, and K. Uchimoto: "Base Induced Reaction of Silacyclobutane with Aldehyde or Epoxide" Tetrahedron Lett.Vol. 31. 6059-6062 (1990)

Y. Takeyama、K. Oshima 和 K. Uchimoto：“硅杂环丁烷与醛或环氧化物的碱诱导反应”Tetrahedron Lett.Vol。

H. Tomioka, K. Hirai, K. Tabayashi, S. Murata, Y. Izawa, S. Inagaki, T. Okajima: "Neighboring Group Participation in Carbene Chemistry. Effect of Neighboring Carboxylate Group on Carbene Reactivities" J. Am. Chem. Soc.Vol. 112. 7692-7702 (1990)

H. Tomioka、K. Hirai、K. Tabayashi、S. Murata、Y. Izawa、S. Inagaki、T. Okajima：“邻近基团参与卡宾化学。邻近羧酸盐基团对卡宾反应性的影响”J. Am。

I. Fujita, Y. Teki, T. Takui, T. Kinoshita, K. Itoh, F. Miko, Y. Sawaki, H. Iwamura, A. Izuoka, and T. Sugawara: "Design, Preparation, and ESR Detection of a Ground-State Undecet(S=5) Hydrocarbon" J. Am. Chem. Soc.Vol. 112. 4074-4075 (1990)

I. Fujita、Y. Teki、T. Takui、T. Kinoshita、K. Itoh、F. Miko、Y. Sawaki、H. Iwamura、A. Izuoka 和 T. Sukawara：“设计、制备和 ESR 检测

Y.Takeyama,K.OshimaK.uchimoto: "Base Induced Reaction of Silacyclobutane with Aldehyde and Epoxide" Tetrahedron Lett.31. 6059-6062 (1990)

Y.Takeyama，K.OshimaK.uchimoto：“硅杂环丁烷与醛和环氧化物的碱诱导反应”四面体快报.31。

T. Tsumuraya, S. Sato, and W. Ando: "Molecular Structures and Reactivities of Digermiranes and Azadigermiridines" Organometallics. Vol. 9. 2061-2067 (1990)

T. Tsumuraya、S. Sato 和 W. Ando：“Digermiranes 和 Azadigermiridines 的分子结构和反应性”有机金属。