2002 Fiscal Year Final Research Report Summary
Development of Highly Efficient Organometallic Catalysis for Short-step Assembly of Complex Moleculer Structures
| Project/Area Number |
12450360
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | Nagoya University |
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Principal Investigator |
ITOH Kenji Nagoya University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (60023149)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAMOTO Yoshihiko Nagoya University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (60283412)
MATSUDA Isamu Nagoya University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (80023266)
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| Project Period (FY) |
2000 – 2002
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| Keywords | Homogeneous Catalysis / Ruthenium / Palladium / Rhodium / Iridium / Multicomponent Coupling / Organometallic Complex |
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| Research Abstract |
1. In the presence of catalytic amounts of Cp*Ru(cod)Cl, unsymmetrical 1,6-diynes possessing a variety of functional groups reacted with electron-deficient tricarbonyl compounds at the ketone C=0 double bonds to selectively afford dienones via electrocyclic ring opening of the expected α-pyrans.
2. The Pd(0)-catalyzed cyclization of electron-deficient diynes and triynes efficiently gave polycyclic aromatic coupounds. Their reaction mechanism was elucidated by means of the characterization of relevant intermediate complexes and density functional calculations of intermediate models.
3. A rhodium-catalyzed method for the synthesis of β-amino esters was accomplished in a one-pot procedure from aldimine, α,β-unsaturated ester and hydosilane.
4. Propargylic-type acetates react readily with enoxysilanes in the presence of a catalytic amount of a cationic iridium complex to give β-alkynyl ketones in high to excellent yields. Substitution at propargyl carbon proceeds exclusively or selectively in most types of propargylic esters. Alternatively, the formation of the allenyl products is predominant in the reaction of esters, which have two phenyl groups on the propargyl carbon.
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