2006 Fiscal Year Final Research Report Summary
Development of Organic Reactions using Interconversion between a Diene-iron Complex and an Allyl-iron Complex
| Project/Area Number |
17550040
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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 |
Organic chemistry
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| Research Institution | Kyushu Institute of Technology |
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Principal Investigator |
OKAUCHI Tatsuo Kyushu Institute of Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60274552)
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| Project Period (FY) |
2005 – 2006
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| Keywords | diene-iron complex / Lewis acid / substitution / η^2-allyl-iron complex |
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| Research Abstract |
Diene-iron complexes shows various characters, such as a protecting group for conjugated dienes etc. However, there are few examples directly using a diene moiety. η^3-Allylcation intermediates are generated when iron complexes are treated with Bronsted acid. The similar intermediate from diene-iron complexes would be formed on treatment of diene-iron complexes with Lewis acid. We found that a diene-iron complex bearing a leaving group at C3 of diene reacted with allyltrimethylsilane in the presence of ^iBuAl(OTf)_2. In this study, we examined whether other diene-iron complexes react with allylsilane in the presence of Lewis acid.
Various acyclic diene-iron complexes bearing methanesulfonyloxy group at C3 of diene reacted with allyltrimetylsilane in the presence of BuAl(OTf)2, and the allylated products were obtained in good yields. Next, the similar reaction using cyclic diene-iron complexes was carried out, but the expected product was not obtained. Thus, the ligand of iron was changed from carbonyl to phoshorus in order to increase the electron density of the diene moiety. The corresponding allylated product was obtained in moderate yield when diene-iron complex bearing trimethy phosphate as a ligand of iron. Furthermore, substitution trifluoromethanesulfonyloxy group at C3 instead of methanesulfonyloxy group increased the yield of the allylated product.
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