1987 Fiscal Year Final Research Report Summary
Development of Novel Synthetic Organic Reactions by Means of Rare Earth Metal Complexes
| Project/Area Number |
61550642
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyushu University |
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Principal Investigator |
FUJIWARA Yuzo Kyushu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (10029481)
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| Co-Investigator(Kenkyū-buntansha) |
ISOMURA Kazuaki Kyushu University, Faculty of Engineering, Assistant Professor, 工学部, 講師 (80037887)
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| Project Period (FY) |
1986 – 1987
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| Keywords | Trichlorolanthanoids as Friedel-Crafts Catalysts / Ytterbium Mediated Reduction of Multiple Bonds / Yb金属による芳香属ケトンの極性変換 / 非対称ピナコール合成 / 再使用可能なフリーデル・クラフツ触媒 |
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| Research Abstract |
By studies on this project, the following novel synthetic reactions are explored by utilizing rare earth metals and their complexes:
1. Trichlorolanthanoid(LnCl_3) Catalyzed Friedel-Crafts Alkylation and Acylation.
LnCl_3 including all the rare earths except Pm, have been found to be good catalysts for Friedel-Crafts alkylation and acylation of aromatic compounds such as benzene and furan. Characteristic feature of those catalysts is that they can be recovered after the reaction without decomposition and can be reused repeatedly.
2. Convenient Reduction of C-C Multiple Bonds Conjugated with Aromatic Rings by PhYbI Complex or Yb Metal.
PhYbI/MeOH or Yb/MeOH causes reduction of aromatic-substituted olefins and acetylenes to give the corresponding alkanes. The use of MeOD gives deuteriated alkanes in quantitative yields.
3. Ytterbium Mediated Synthesis of Symmetrical and Unsymmetrical Pinacols from Carbonyl Compounds.
Reaction of Yb metal with aromatic ketones such as benzophenone gives in situ metallacycle intermediates(KA) which undergo coupling with a variety of ketones to give symmetrical and unsymmetrical pinacols in high yields. This is the first example of the reaction in which polarity of ketones is changed from positive to negative by Yb. Furthermore it has been found that the metallacycle intermediates can react with not only ketones but also a variety of electrophiles such as nitriles, epoxides, CO_2 etc.
Through this project, rare earth mediated novel and very useful reactions have been developed.
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Research Products
(13 results)
