| Project/Area Number |
16205014
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
MITSUDO Take-aki Kyoto Univ., Graduate School of Eng., Professor, 工学研究科, 教授 (90026344)
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| Co-Investigator(Kenkyū-buntansha) |
KONDO Teruyuki Kyoto Univ., Graduate School of Eng., Associate Professor, 工学研究科, 助教授 (20211914)
WADA Kenji Kyoto Univ., Graduate School of Eng., Lecturer, 工学研究科, 講師 (10243049)
URA Yasuyuki Kyoto Univ., Graduate School of Eng., Instructor, 工学研究科, 助手 (40335196)
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| Project Period (FY) |
2004 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥51,350,000 (Direct Cost: ¥39,500,000、Indirect Cost: ¥11,850,000)
Fiscal Year 2005: ¥9,750,000 (Direct Cost: ¥7,500,000、Indirect Cost: ¥2,250,000)
Fiscal Year 2004: ¥41,600,000 (Direct Cost: ¥32,000,000、Indirect Cost: ¥9,600,000)
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| Keywords | Environmentally Benign Catalyst / Ruthenium Complex / Carbon-Carbon Bond Cleavage / Cocyclotrimerization / Codimerization / Acrylic Compound / Phenolate Complex / Aqua Complex / ルテニウム錯体触媒 / アルキン / カルボニル化反応 / ヒドロキノン / スルフェンアミド / シクロブテノン / フェノール / オキソシクロヘキサジエニル |
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| Research Abstract |
The creation of novel transition metal complexes which show high catalytic performance is essential for development of highly atom-economical and environmentally benign synthetic methods without the formation of byproducts. In this study, we first succeeded in preparation of novel Ru(0) complexes bearing arenes, p-quinones, and tridentate pyridyl ligands via selective displacement of either 1,3,5-cyclooctatriene (cot) or dimethyl fumarate (dmfm) ligands in Ru(η^6-cot)(η^2-dmfm)_2 (1). The stoichiometric reaction of 1 with phenol gave novel Ru(II) phenolate complexes, while the reaction of 1 with water in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) gave a novel chiral Ru(0) aqua complex, Ru(η^2-dppe)(η^2-dmfm)_2(H_2O) (2). The structures of all novel complexes were clearly determined by X-ray crystallography. Optical resolution of rac-2 was successfully performed by HPLC equipped with a chiral column.
In addition, we have developed the following novel catalytic reactions characteristic to ruthenium ; 1)formal [4+2] cycloaddition of alkynes with electron-deficient alkenes to cyclohexenedicarboxylates via isomerization of alkynes and successive Diels-Alder reaction, 2)[2+2+2] cocyclotrimerization of three different alkynes (dimethyl acetylenedicarboxylate, 1-decyne and 3-hexyne), 3)regio- and stereoselective linear codimerization of 2-norbornenes with acrylic compounds, 4)synthesis of 2-alkylidenetetrahydrofurans by codimerization of dihydrofurans with α,β-unsaturated esters. All these ruthenium-catalyzed reactions offered the synthetic methods for novel functional monomers with high atom-efficiency.
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