| Co-Investigator(Kenkyū-buntansha) |
OKAZAKI Renji Professor, Department of Chemistry University of Tokyo, 教授 (70011567)
ANDO Wataru Professor, Department of Chemistry University of Tsukuba, 化学系, 教授 (30008429)
TAKEUCHI Kenichi Professor, Department of Petroleum Chemistry Kyoto University, 工学部, 教授 (50026358)
TSUNO Yuho Professor, Department of Chemistry Faculty of Science, Kyushu University, 理学部, 教授 (10029845)
MOROKUMA Keiji Professor, Institute for Molecular Sciences, 教授 (40111083)
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| Research Abstract |
This co-operative research has been carried out by organizing four subbgroups. (1)Electronic Aspects of Reaction mechanism and Path The reaction paths of the cyclization of penta-1,4-dienes and the additions to fullerene were elucidated theoretically by ab initio MO calculations. On the other hand, the resonance demands in the solvolysis of benzyl derivatives were analyzed very exactly and correlated to its mechanism. Molecular interactions involved in the organic reaction mechanism were studied both from theoretical and kinetical points of view.
(2)Steric Course and Stereoselectivity of Reactions By use of molecular mechanics, steric hindrance was evaluated quantitatively and the steric course of the reactions of trishomocubanes was estimated. The sterically congested reaction field was desigened in STECAR concept and in the BINAP-RU hydrogenation.
(3)Structures and Interactions in Reaction Intermediates The structures and properties of stable cations, such as alpha-arylvinyl cation and bicyclic alpha-keto-cations, and polyradicals were elucidated. In contrast, very fast electron transfer rection and very short-lived photo-excited states were identified by laser photolysis and other new techniques. Sonochemical method was applied to the switching of reactions.
(4)Reactions of Heteroatom-Cntaining and Biological Molecules Silicenium ions, polysilacyclo- alkynes, hypervalent compounds, chiral bismuthines, [3,3]metacylophanes, and other novel compounds were designed and their applications were pursued. On the other hand, reaction mechanisms of model enzymes were studied kinetically.
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