2007 Fiscal Year Final Research Report Summary
Synthesis of Chirality Controlled Optically active Ferrocenes and Their Application to Catalytic Asymmetric Synthesis
| Project/Area Number |
18550046
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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 | Chuo University |
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Principal Investigator |
FUKUZAWA Shin-ichi Chuo University, Faculty of Science and Engineering, Professor (50173331)
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| Co-Investigator(Kenkyū-buntansha) |
KIKUCHI Satoshi Chuo University, Faculty of Science and Engineering, Assistant Professor (60407872)
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| Project Period (FY) |
2006 – 2007
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| Keywords | ferrocene / chiral ligand / phosphine ligand / Taniaphos / bridged ferrocene / allylic alkvlation / allylic amination / ortho lithiation |
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| Research Abstract |
The 1, 5-dilithiation of o-TMS blocked (dimethylamino) phenylmethylferrocene with tBuLi unexpectedly occurred and the 1, 5-dilithiated ferrocene was trapped by halogen followed by removal of the TMS group to give the 1, 5-dihaloferrocene in a reasonable yield. The 1, 5-diiodoferrocene was converted into Taniaphos ligand by the sequencial of dilithiation and trapping with Ph_2PCl. The methoxy 1, 5-diphosphane was obtained by the inversive substitution of the dimethylamino group by NaOMe and subsequent dilithiation and trapping with Ph_2PC 1. The homoannularly bridged ferrocene was prepared by the intramolecular coupling of the 1, 5-dilithioferrocene mediated by Fe(acac)_3. Its benzene ring underwent ortho-lithiation by tBuLi, and subsequent trapping with Ph_2PCl produced the corresponding aminophosphine. The aminophosphine which has the phosphinyl group on the cyclopentadienyl group was prepared by intramolecular coupling of 1, 5-dilithiated Ph-PPFA mediated by Fe(acac)_3. The new N, P-ligands were applied to the benchmark palladium complex-catalyzed allylic alkylation and amination of the 1, 3-diphenyl-2-propenyl acetate and was found to give good results (good yields with high enantioselectivities, up to 96% ee).
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