1988 Fiscal Year Final Research Report Summary
DEVELOPMENT OF NEW REGIO AND STEREOSELECTIVE REACTIONS FOR ORGANIC SYNTHESIS
| Project/Area Number |
61470025
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Kyoto University |
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Principal Investigator |
KAJI Aritsune Professor (Faculty of Science), 理学部, 教授 (10025223)
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| Co-Investigator(Kenkyū-buntansha) |
TANAKA Kazuhiko Assistant (Faculty of Science), 理学部, 助手 (00025446)
TANIKAGA Rikuhei Assistant Professor (Faculty of Science), 理学部, 助教授 (60025377)
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| Project Period (FY) |
1986 – 1987
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| Keywords | ALKYLATION OF FURAN / DENITRO-ALKYLATION / ORIENTATION CONTROL OF DIELS-ALDER REACTION / SYNTHON OF ALKYNE / CYCLOPROPANECARBOXYLIC ACID / HOMOBUTENOLIDE / YEAST REDUCTION OF KETON / 不斉アルコール合成 |
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| Research Abstract |
The research has been successfully performed as follows:
1. Substitution of Nitro Group on Nitrofurancarboxylic Esters: Ethyl 2-nitrofuran-5-carboxylate were easily converted to ethyl 3-alkylfuran-5-carboxylate by the reaction with an anion of nitroalkane followed by the treatment with tributyltin hydride. THus, a new denitro-alkylation reaction on furan has been presented.
2. New Orientation Control on the Deils-Alder Reaction: 1-Nitro-2-phenylsulfonyl-1-alkenes were found to be strong dienophile. It reacted with 2-methyl-2-butene to give a cyclohexene. The product was treated with tributyltin hydride to give 1-methyl-4-alkylcyclohexa-1,4-diene only.
3. New Convenient Synthesis of Cyclopropanecarboxylic Acid: When 2-phenylthionethyl-3-phenylthiopropioanilide was converted to its dianion, 2-phenylthiocyclopropanecarbanilide was obtained spontaneously. The product could be derived to highly functional derivatives by the reaction of its dianion and and electrophiles such as aldehydes.
4. New Synthesis of Optically Active Alkohols with 100% Enantio Excess (e.e.): 1-Chlosyl-3-chloroacetone was easily reduced by commercial Baker's Yeast to give (R)-1-chlosyl-o-chloropropan-2-ol with 100% e.e.. The yield was 85%. This propanol could be alkylated at 3-position via its epoxide with nucleophile, and also successfully be alkylated at 1-position via its dianion. In both of the alkylation, the configuration of alcohol was kept at 100% e.e..
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