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Development and Application of New Transformations of Organosulfur Compounds Utilizing Magnesium Amides

Research Project

Project/Area Number 07651032
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionTottori University

Principal Investigator

KOBAYASHI Kazuhiro  Tottori University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90161976)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1995: ¥1,800,000 (Direct Cost: ¥1,800,000)
KeywordsMagnesium amides / Sulfides / unsymmetrical dithioacetals / Sulfoxides / alpha-Sulfenylalkylation / Asymmetric synthesis / Pummerer reaction / Sulfonium ions / 還元 / α-アミノアルデヒド / チオール
Research Abstract

It was found that sulfoxides bearing hydrogens at the alpha-position only (RSOCH_2R^1) reacted with the tetramethylpiperidinomagnesium reagent, which was generated in situ by treatment of 2,2,6,6-tetramethylpiperidine with ethylmagnesium bromide in refluxing diethyl ether, at room temperature to produce the corresponding dithioacetals (RSCHR^1SR). The treatment of sulfoxides bearing hydrogens both at the alpha- and beta-positions (RSOCHR^1CHR^2R^3) with the magnesium amide was found to afford the corresponding vinyl sulfides (RSCR^1=CR^2R^3) accompanying the corresponding dithioacetals. The pathways leading to the products involving the formation of the sulfur stabilized carbonium ion intermediates were elucidated, and these reactions were extended to syntheses of a range of organosulfur compounds.
The reaction of sulfoxides bearing alpha-hydrogen (s) (RSOCHR^1R^2) with the diisopropylaminomagnesium reagent, which was generated in situ by the treatment of diisopropylamine with an excess … More amount of appropriate Grignard reagents (R^3MgBr), resulted in the formation of the corresponding sulfides (RSCR^1R^2R^3). Optically active sulfides could be obtained up to 75% e.e. by using optically active sulfoxides or secondary amines.
The (diisopropylamino) magnesium reagent, generated from diisopropylamine and ethylmagnesium bromide, was treated with thiols (R^4SH) prior to the interaction with sulfoxides bearing hydrogen (s) at the alpha-position (R^1SOCHR^2R^3) to afford unsymmetrical dithioacetals (R^1SCR^2R^3SR^4).
The treatment of vinyl sulfoxides (PhSOCHR^1=CHR^2) with (dialkylamino) magnesium reagents, generated from secondary amines (R^3_2NH) and ethylmagnesium bromide, proved to give unsymmetrical beta- (N,N-dialkylamino) dithioacetals [(PhS) _2CHR^1CHR^2NR^3_2]. The reaction in the presence of an appropriate thiol (R^4SH) lead to the formation of the corresponding unsymmetrical beta- (N,N-dialkylamino) dithioacetals [(PhS) (R^4S) CHR^1CHR^2NR^3_2].
Tretment of the (diisopropylamino) magnesium reagent with enemines, derived from various ketones and aldehydes, prior to the interaction with sulfoxides bearing alpha-hydrogens gave the corresponding alpha- (alpha-alkylthio) alkylated ketones and aldehydes. Less

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (5 results)

All Other

All Publications (5 results)

  • [Publications] 小林和裕: "Reductive α-Substitution of Sulfoxides with Grignard Reagents Promoted by a Magnesium Amide" Bulletin of the Chemical Society of Japan. 69. 441-443 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 小林和裕: "An Efficient Synthesis of Unsymmertrical Dithioacetals from Sulfoxides and Thiols by the Magnesium Amide-Induced Pummerer-Type Reaction" Bulletin of Chemical Society of Japan. 69. 2645-2647 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Kazuhiro Kobayashi: "Reductive alpha-Substitution of Sulfoxides with Grignard Reagents Promoted by a Magnesium Amide" Bulletin of the Chemical Society of Japan. 69. 441-443 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Kazuhiro Kobayashi: "An Efficient Synthesis of Unsymmetrical Dithioacetals from Sulfoxides and Thiols by the Magnesium Amide-Induced Pummerer-Type Reaction" Bulletin of the Chemical Society of Japan. 69. 2645-2647 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 小林 和裕: "An Efficient Synthesis of Unsymmetrical Dithioacetals from Sulfoxides and Thiols by the Magnesium Amide-Induced Pummerer-Type Reaction" Bulletin of the Chemical Society of Japan. 69・9. 2645-2647 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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