1990 Fiscal Year Final Research Report Summary
Chemical Behaviors and Synthetic Applications of Hypovalent Organic Metastable Species Under WellーControlled Conditions
| Project/Area Number |
01300011
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| Research Category |
Grant-in-Aid for Co-operative Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
広領域
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| Research Institution | Kyoto University |
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Principal Investigator |
TAKAYA Hidemasa Kyoto Univ., Faculty of Engineering, Professor, 工学部, 教授 (40022644)
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| Co-Investigator(Kenkyū-buntansha) |
IWAMURA Hiizu the Univ. of Tokyo, Faculty of Science, Professor, 理学部, 教授 (10011496)
SUZUKI Hitomi Kyoto Univ., Faculty of Science, Professor, 理学部, 教授 (50025342)
IBATA Toshikazu Osaka Univ., College of General Education, Professor, 教養部, 教授 (80029644)
ISHIKAWA Mitsuo Hiroshima Univ., Faculty of Engineering, Professor, 工学部, 教授 (20025985)
ANDO Wataru Tsukuba Univ., Department of Chemistry, Professor, 化学系, 教授 (30008429)
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| Project Period (FY) |
1989 – 1990
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| Keywords | metal-carbene complex / carbene / silylene / qermylene / arylcarbene / MO calculation / alkylfluorocarbenoid / allylcarbene-Pt |
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| Research Abstract |
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
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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
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[Publications] 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)
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