| Project/Area Number |
05236102
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Research Institution | The University of Tokyo |
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Principal Investigator |
OKAZAKI Renji The University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (70011567)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAMOTO Yosuke Hiroshima University, Faculty of Science, Associate Professor, 理学部, 助教授 (50158317)
MIGITA Toshihiko Tokai University, School of High Technology for Human Welfare, Professor, 開発工学部, 教授 (40008412)
HOSOMI Akira University of Tsukuba, Department of Chemistry, Professor, 化学系, 教授 (00004440)
BABA Akio Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (20144438)
NOYORI Ryoji Nagoya University, Faculty of Science, Professor, 理学部, 教授 (50022554)
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| Project Period (FY) |
1993 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥68,800,000 (Direct Cost: ¥68,800,000)
Fiscal Year 1995: ¥23,400,000 (Direct Cost: ¥23,400,000)
Fiscal Year 1994: ¥23,400,000 (Direct Cost: ¥23,400,000)
Fiscal Year 1993: ¥22,000,000 (Direct Cost: ¥22,000,000)
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| Keywords | Organosilicon compounds / Organogermanium compounds / Organotin compounds / Organoantimony compounds / Organobismuth compoun / Assymetric alkylation / Kinetic stabilization / X-ray crystallograhy / ゲルマンテロン / 不斉触媒反応 / 高配位スズ化合物 / ヒドリドンリカート / 高配位化合物 / オルトキノジメタン |
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| Research Abstract |
The organic compounds of main group elements belonging to groups 12-15 were studied. (1) Heavier element analogs of ketones containing a Ge=X bond (X=S,Se, Te) were synthesized taking advantage of kinetic stabilization of a 2,4,6-tris [bis (trimethylsilyl) methyl] phenyl group and their structures and reactivities were investigated (Okazaki). (2) Asymmetric alkylation of aldehydes using alkylzinc compounds of an optically active amino alcohol, (-) - (2S) -3-exo- (dimethylamino) -isoborneol, was studied. The mechanism of the reaction was elucidated by examing the thermodynamic stability of the dimer of the zinc reagent, and the nonlinearity effect of the equilibrium constants (Noyori). (3) A new type of tin hydrides Bu_2SnXH (X=F,Cl, Br, I) was developed and the effect of halogen and/or complexation on the selectivity and reduction ability was studied (Baba). (4) High coordinate silicon compounds were synthesized as synthons of allyl anion, hydride ion, and vinyl anion. For example, allylsilanes underwent either allylation or [2+2] cycloaddition depending on the receptors (Hosomi). (5) Nitrogen containing bicyclic germanium and tin compounds were synthesized in order to study the ability of group 14 element compounds as a carbon nucleophile. The Pd catalyzed coupling reaction with halogenated compounds was developed and applied to the synthesis of natural products (Migita). (6) Five coordinate organoantimony and bismuth compound were prepared and their structures were established by X-ray crystallographic analysis. The pseudorotation of these compounds were accelerated by a nucleophile such as a fluoride ion (Yamamoto).
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