| Project/Area Number |
03555178
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
TAKAYA Hidemasa Kyoto Univ. Fac. of Engineering Professor, 工学部, 教授 (40022644)
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| Co-Investigator(Kenkyū-buntansha) |
SAYO Noboru Takasago Chemical Co. Sub-reader, 総合研究所, 副主任
KUMOBAYASHI Hidenori Takasago Chemical Co. Research Reader, 総合研究所, 室長
TAMAO Kyoko Kyoto Univ., Fac, of Eng., Assistant, 工学部, 助手 (60222197)
OHTA Tetsuo Kyoto Univ., Fac. of ENG., Assistant, 工学部, 助手 (50213731)
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| Project Period (FY) |
1991 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥17,100,000 (Direct Cost: ¥17,100,000)
Fiscal Year 1992: ¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 1991: ¥13,300,000 (Direct Cost: ¥13,300,000)
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| Keywords | BINAP / Asymmetric / Hydrogenation / Catalysis / Ruthenium / Iridium / bete-butyrolactone / arpha-keto esters / ロジウム錯体触媒 / ビスホスファイト配位子 / α,β-不飽和カルボニル化合物 / 官能基選択的水素化 / チオフェン-3-オ-ル / BINAP-Ru3核錯体 / 錯体の溶液中での挙動 |
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| Research Abstract |
Several BINAP derivatives have been prepared and their donor-acceptor propeties have been elucidated. New cationic complexes [RuX(binap)(arene)]Y were synthesized in high yields and their catalytic abilities as well as their behaviors in solution have been investigated. Optimization of the reaction conditions of asymmetric hydrogenation of methyl 2-benzamidomethy1-3-oxobutanoate by use of these complexes as catalysts afforded the corresponding alcohol in 98% de and 99% ee. Asymmetric hydrogenation of alpha-alkylidenecyclopentanones, alkylidenelactones, alkenyl ethers, and alpha-keto esters has also been performed in high enantioselectivities. Hydrogenation of various 1,2-benzocycloalkanones and 3-thiacycloalkanones catalyzed by newly developed BINAP-ir(I)-aminophosphine systems afforded the corresponding secondary alcohols in up to 96% ee.
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