Organic Synthesis Using Electrochemical Functionalization of an Unactivated Carbon Position
| Project/Area Number |
62550620
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Hokkaido University |
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Principal Investigator |
TOKUDA Masao Faculty of Engineering, Hokkaido University, 工学部, 助教授 (80001296)
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| Co-Investigator(Kenkyū-buntansha) |
ORITO Kazuhiko Faculty of Engineering, Hokkaido University, 工学部, 助手 (20109482)
SUGINOME Hiroshi Faculty of Engineering, Hokkaido University, 工学部, 教授 (00000779)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1988: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1987: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | Functionalization of Unactivated Carbon Position / Remote Functionalization / Anodic Acetamidation / Anodic Oxidation / Steroid / アリル位酸化 / アリル位アセトキシル化 / ステロイドオレフィン / アセトアミド化 / 6α-アセトアミドコレスタン / 12-アセトアミドコレスタン |
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| Research Abstract |
1. Remote acetamidation of steroids by anodic oxidation.
Anodic oxidation of 5 -cholestan-3 -yl esters with a carbonyl or a m-iodophenyl group in their 3 -substituents at a controlled potential of +2.3 +2.7V vs Ag/AgNO_3 in acetonitrile gave the corresponding 6 -acetamidated cholestanyl esters in 7 26% yields. The structure and the stereochemistry of the product were confirmed by comparison with an authentic specimen which was prepared via nine steps from cholesterol in a total yield of 4.8%. Reaction pathways involving an intramolecular abstraction of an unactivated hydrogen were proposed from a study of cyclic voltammetry.
2. Anodic acetamidation of cholestanes and androstane.
Anodic oxidation of the steroids having no 3 -substituents in acetonitrile also gave the 6 -acetamidated cholestanes and androstane. The yield of the product was found to be enhanced to 36% by an addition of 2-butanone.
3. Other functionalizations of steroids.
Chlorination of the C-9 position of steroids was successfully carried out by anodic oxidation of 5 -cholestan-3 -yl m-iodobenzoate in the presence of chloride ion. Anodic oxidation of steroidal olefins in the presence of Co(OAc)_2 and NaOH lead to a successful acetoxylation of their allylic carbons.
4. Allylic oxidation of steroids.
An allylic methylene of the steroidal olefins was successfully transformed into a carbonyl group by anodic oxidation in the presence of sodium hydroxide or n-hydroxyphthalimide (NHPI)/sodium hydroxide.
5. Chlorinarion of an unactivated carbon of aliphatic compounds.
A reaction of the aryl ester of aliphatic alcohol with sulfuryl chloride gave a remote-chlorinated product.
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Report
(3 results)
Research Products
(16 results)
