1988 Fiscal Year Final Research Report Summary
Novel Synthetic Methods of -Amino Acids and -Hydroxy Acids Using Transition Metal Catalysts
| Project/Area Number |
62850147
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
YAMAMOTO Akio Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Professor, 資源化学研究所, 教授 (30016711)
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| Co-Investigator(Kenkyū-buntansha) |
IZAWA Kunisuke Basic Research Department, Central Research Laboratories, Ajinomoto Co. Inc., Se, 中央研究所基礎研究部, 主任研究員
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| Project Period (FY) |
1987 – 1988
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| Keywords | Double carbonylation reactions / alpha-Amino acid synthesis / α-ヒドロキシ酸合成 |
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| Research Abstract |
Recently we found that various organic halides including aryl and alkenyl halides can be converted into alpha-keto acid derivatives such as alpha-keto amides and alpha-keto esters on reactions with carbon monoxide and nucleophiles (secondary amines and alcohols) in the presence of catalytic amounts of palladium complexes. In this study novel alpha-amino acid and alpha-hydroxy acid syntheses utilizing these double carbonylation reactions have been examined.
(1) Mechanisms and scope of applications of the double carbonylation reactions have been studied in detail.
(2) Stoichiometric double carbonylation of alpha-olefins to afford beta,gamma-unsaturated alpha-keto amides has been performed by using an aminopalladation reaction.
(3) Novel synthetic reactions which convert aromatic aldehydes and hydrocarbons into alpha-keto amides have been developed.
(4) A variety of aromatic alpha-keto acids can be synthesized in good yields by hydrolysis of alpha-keto amides prepared by the double carbonylation reactions of aryl halides.
(5) The alpha-keto acids thus obtained are converted into corresponding alpha-amino acids in over 90% yields by treatment with phenylhydrazine followed by palladium-catalyzed hydrogenation of resulting phenylhydrozones of the alpha-keto acids.
(6) Highly selective asymmetric reduction of various para- and meta-substituted benzoylformic acid esters to give optically active mandelic acid ester derivatives is performed by using a baker's yeast (Saccharomyces cervisiae).
(7) Alpha-keto acids can be reduced to corresponding alpha-hydroxy acids in aqueous alkaline solutions containing methanol or formaldehyde.
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