1999 Fiscal Year Final Research Report Summary
Search for New Synthetic Reactions using Acylzirconocene Complex as an "Unmasked" Acyl Anion
| Project/Area Number |
10672000
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | Tokyo University of Pharmacy and Life Science |
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Principal Investigator |
HANZAWA Yuji Tokyo University of Pharmacy and Life Science, School of Pharmacy, Associate Professor, 薬学部, 助教授 (10096688)
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| Project Period (FY) |
1998 – 1999
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| Keywords | Early transition metal / Acylzirconocene complex / Catalytic reaction / Coupling reaction / Regioselective reaction / Asymmetric synthesis |
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| Research Abstract |
In our ongoing research project on new synthetic reactions using acylzirconocene complex, we have exploited enormous possibilities of acylzirconocene complex for organic synthesis. During the past term of the project we established several quite new synthetic reactions in which acylzirconocene chloride reacted with aldehyde in the presence of a stoichiometric amount of Lewis acid to give a-ketol derivatives. It is the first example that the acylzirconocene chloride reacts as an "unmasked" acyl anion. We also found a Pd-catalyzed reaction of acylzirconocene chloride with organic halides to give ketone derivatives. Moreover, in the Pd-catalyzed conditions, acylzirconocene complex adds to α, β-unsaturated ketones, regioselectively. In the 1, 2-selective addition conditions, an enantioselective addition of the "unmasked" acyl anion was achieved for the first time by the use of chiral phosphine ligand. Although the asymmetric induction (66% ee) in the present reaction is not satisfactorily high yet, we are currently continuing the research to find more effective chiral ligand for zirconium metal complex.
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