Innovative Structure Conversion of Optically Active Amino Acids by Electrochemical Oxidation and Its Utilization in Organic Synthesis
| Project/Area Number |
09450335
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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 |
有機工業化学
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| Research Institution | KYUSHU UNIVERSITY (1998-1999)
Nagasaki University (1997) |
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Principal Investigator |
MATSUMURA Yoshihiro Kyushu University, Institute for Fundamental Research of Organic Chemistry, Professor, 有機化学基礎研究センター, 教授 (60026309)
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| Co-Investigator(Kenkyū-buntansha) |
真木 俊英 長崎大学, 薬学部, 助手 (10291535)
木下 敏夫 長崎大学, 薬学部, 助教授 (60039641)
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| Project Period (FY) |
1997 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥13,100,000 (Direct Cost: ¥13,100,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1997: ¥8,600,000 (Direct Cost: ¥8,600,000)
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| Keywords | Electrochemical oxidation / Optical activity / α-Amino acid / Hofmann rearrangement / Alkylation / Memory of chirality / 不斉合成 / 選択性 / カルバメート / 炭素間結合形成 / シクロプロパン化 |
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| Research Abstract |
Synthesis of optically pure organic compounds is one of topics in current organic synthesis. In this study, electrochemical oxidation was used as a key step for the transformation of easily available α-amino acids to new optically active intermediates, which were further elaborated in organic synthesis as described below.
(1) L-Protein and L-lysine derivatives were converted to optically active α-alkylproline and α-alkylpipecolinic acid derivatives by using electrochemical oxidation as a key step. (2) Optically active acyclic ω-carboxyl-α-alkyl-α-amino acids and new optically active auxiliary were prepared through oxidation products that were prepared by electrochemical oxidation of L-lysine derivative. (3) Optically active β-amino acid (d-threo-methylphenidate) was prepared with a high enantioselectivity by the carbon-carbon bond formation between a-methoxypiperidine derivative and N-phenylacetyloxazolidinone prepared from L-valine. (4) A new reaction condition appropriate to the Hofmann rearrangement was exploited. The reaction condition was created by using an electrochemical method in which 2,2,2-trifluoroethanol (TFEOH) was used as a solvent. Under the reaction condition, L-Glutamine ester derivative was efficiently converted to 2,4-diaminobutyric acid ester without a loss of the original optical purity. Furthermore, tirflouroethoxycarbonylamines, the Hofmann rearrangement products in TFEOH, were found to be precursors for unsymmetrical ureas. (5) Memory of chirality was observed in the non-Kolbe reaction of some kinds of optically active cyclic α-amino acids. (6) An efficient reagent for the Cα-Cβ bond of cyclic amino compounds was exploited and it was applied to the ring opening of L-pipecolinic acid derivative.
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Report
(4 results)
Research Products
(19 results)
