2005 Fiscal Year Final Research Report Summary
Development of Highly Efficient Synthetic Organic Reactions with Indium-transition Metal Combined Reagents
| Project/Area Number |
14340195
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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 |
Organic chemistry
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| Research Institution | Nagoya Institute of Technology |
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Principal Investigator |
ARAKI Shuki Nagoya Institute of Technology, Graduate School of Engineering, Professor, 工学研究科, 教授 (30115670)
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| Co-Investigator(Kenkyū-buntansha) |
KAWAI Msao Nagoya Institute of Technology, Graduate School of Engineering, Professor, 工学研究科, 教授 (60161270)
YAMAMURA Hatsuo Nagoya Institute of Technology, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (80220440)
HITASHITA Tsunehisa Nagoya Institute of Technology, Graduate School of Engineering, Research Associate, 工学研究科, 助手 (50345948)
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| Project Period (FY) |
2002 – 2005
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| Keywords | Indium / Transition-metal / Palladium / Nickel / Organometallic Compounds / Selectivity / Carbon-carbon Bond Formation / Gallium |
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| Research Abstract |
The synthetic utility of the combination of organoindium compounds and transition-metal complexes, such as nickel and palladium compounds, has been studied in order to develop new synthetic reactions and novel functional group transformations. The results obtained in this project can be summarized as follows.
1.π-Allylpalladium complexes have been found to be converted readily to allylic indium reagents by the reductive transmetallation with indium(I) iodide. This reaction can be applied also for the corresponding π-allylnickel complexes, and a variety of allylic compounds including allylic alcohol themselves can be used without any activation. The allylic indium reagents prepared from π-allylpalladium and π-allylnickel complexes showed slightly different behavior. The methodology developed here provides a novel and useful environmentally benign process.
2.The reactions of three-membered ring compounds, such as cyclopropenes, epoxides, and azirines, with allylic indium reagents have been systematically studied. These reactions gave a various type of products including some rearranged compounds. Their reaction mechanisms were investigated and the regio- and stereoselectivity were discussed.
3.Allylic radicals have been found for the fist time to be generated easily by the photolysis of allylic indium reagents. Intramolecular cyclization reactions follow in high yields to furnish various carbocyclic and heterocyclic compounds. The reaction mechanism and the effects of the ligands on indium and the reaction solvents were investigated in detail.
4.The synthetic use of gallium compounds, another member of the group 13 elements, has been investigated and their similarity in the reactivity and reaction behavior to the corresponding indium compounds has been discussed.
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Research Products
(28 results)
