2005 Fiscal Year Final Research Report Summary
Synthetic studies on novel catalysts incorporating multi planar-chiral units
| Project/Area Number |
14350479
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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 | Waseda University (2005)
Meiji University (2002-2004) |
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Principal Investigator |
KANOMATA Nobuhiro Waseda University, Faculty of Science and Engineering, Professor (40221890)
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| Project Period (FY) |
2002 – 2005
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| Keywords | Stereocontrol of planar chirality / Cyclophane synthesis / Samarium iodide / Intramolecular pinacol coupling / Multi planar-chiral molecules / Phase transfer catalysts / Asymmetric alkylation / Crystallization-induced asymmetric transformation |
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| Research Abstract |
This project aimed the new development of efficient synthetic methodologies to provide novel planar-chiral molecules and design/synthesis of multi planar-chiral molecules as novel phase transfer catalysts.
We have accomplished novel samarium-mediated intramolecular pinacol coupling for synthesis of a series of cyclophanediols in up to 64% yield which were transformed to planar-chiral[n] paracyclophanes(8-12). We have also developed stereocontrol of planar-chiral[11] paracyclophanes by using crystallization-induced asymmetric transformation. Synthesis of a series of[n] parapyridinophanes was also developed by the reaction of(vinylimino) phosphorane intermediates.
These planar-chiral pyridinophane and cyclophane molecules were transformed to multi planar-chiral ammonium salts and their asymmetric alkylation reactions were investigated as asymmetric phase transfer catalysis. Moderate enantioselectivity was observed with up to 75% ee for benzylation of a glycin derivative. We have thoroughly examined the catalytic activities of the pyridinophane and the cyclophane catalysts and the former showed the better enantioselectivities for asymmetric alkylation reactions.
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