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Development of Novel Selective Reactions Using Neighboring Group Effect of a Sulfenyl Group.

Research Project

Project/Area Number 06453132
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

SAIGO Kazuhiko  The University of Tokyo, Graduate School of Engineering, Professor, 大学院・工学系研究科, 教授 (80016154)

Project Period (FY) 1994 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1996: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1994: ¥3,600,000 (Direct Cost: ¥3,600,000)
KeywordsNeighboring Group Effect / Sulfenyl Group / Aldol Reaction / Cationic Cyclozation / Episulfonium Ion / Epoxide / Pheromone / Amino Group / 隣接基関与 / Sharpless酸化 / Lewis酸 / カチオン / カチオン環化反応 / スルホン / 高次有機銅錯体 / アセチレン
Research Abstract

This reserch project is concerned with the development of selective reactions applying the neighboring group effect of a sulfenyl group. First, we tried remote asymmetric induction by the neighboring group participation of a sulfenyl group toward the delta-position. As result, 2-[1-(mesitylthio) alkyl]benzaldehydes and their dimethyl acetals reacted with silylated carbon nucleophiles under Lewis acidic conditions to give the corresponding aldol adducts with high diastereoselectivity, and in some cases, the product was obtained as almost a single diastereomer.
Next, the reaction of episulfonium ions generated via neighboring group participation was investigated. Episulfonium ions with an appropriate intramolecular nucleophilic olefin part gave cyclized products, 5-or 6-membered ring carbocycles, with high diastereoselectivity. This reaction is useful for the synthesis of terpenes and steroids.
The reaction of glycidyl sulfides, which have a sulfenyl group, participating only at C-2, with trialkylaluminum showed definite C-2 selectivity for uncleophilic ring-opening and gave C-2 alkylated products exclusively with the complete retention of the configuration at the C-2. Upon applying the present reaction, an aggregation pheromone of African Palm Weevil was stereoselectively synthesized in short steps.
Amino groups are also known to participate to the neighboring cationic center. Then, similar reactions were carried out with glycidyl amines ; alkylation, alkynylation, and hydride reduction occurred regioselectively at the C-2 position with the retention of the configuration at the C-2.

Report

(4 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] Y.Hashimoto: "Remote Asymmetric Induction Using Neighboring Group Participation of a Sulfenyl Group" Tetrahedron. 50. 8317-8336 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 橋本幸彦: "隣接基関与を利用する選択的合成反応" 有機合成化学協会誌. 53. 116-121 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu: "Highly Stereoselective Catimic Cyclization Assisted by a Sulfenyl Group. Scope,Limitation,and Mechanism" J.Org.Chem.61. 494-502 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu: "α-Sulfenyl-Directed Ring-Opening Reactions of Epoxides : 1.Highly Regio-and Stereoselective Reaction with Organo-Aluminum Reagents and Application to the Synthesis of an Aggregation Pheromone" Bull.Chem.Soc.Jpn.69. 2095-2105 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu: "Regio-and Stereoselective Ring-Opening Reaction of 2,3-Epoxy Amines with Organo-aluminum Reagents Leading to 2-Substituted 3-Amino Alcohols" Tetrahedron Lett.37. 6177-6180 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Hashimoto, Y.Sato, N.Takeshita, K.Kudo, and K.Saigo: ""Remote Asymmetric Induction Using Neighboring Group Participation of a Sulfenyl Group"" Tetrahedron. 50. 8317-8336 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Hashimoto, K.Kudo, and K.Saigo: ""Selective Synthetic Reactions Applying Neighboring Group Participation"" Yuki Gosei Kagaku Kyokai Shi. 53. 116-121 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu, K.Kudo, Y.Hashimoto, and K.Saigo: ""Highly Stereoselective Cationic Cyclization Assisted by a Sulfenyl Group. Scope, Limitation, and Mechanism"" J.Org. Chem.61. 494-502 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu, Y.Hashimoto, K.Kubo, and K.Saigo: ""alpha-Sulfenyl-Directed Ring-Opening Reactions of Epoxides. 1. Highly Regio-and Stereoselective Reaction with Organo-Alumminum Reagents and Application to the Synthesis of an Aggregation Pheromone"" Bull. Chem. Soc. Jpn.69. 2095-2105 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu, Y.Hashimoto, and K.Saigo: ""Regio-and Stereoselective Ring-opening Reaction of 2,3-Epoxy Amines with Organo-aluminum Reagents Leading to 2-Substituted 3-Amino Alcohols"" Tetrahedron Lett.37. 6177-6180 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Liu: "Highly Stereoselective Cationic Cyelization Assisted by a Sulfenyl Group.Scope,Limitation,and Mechanism" J.Org.Chem.61. 494-502 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] C.Liu: "α-Sulfenyl-Directed Ring-Opening Reactions of Epoxides,1.Highly Regio-and Stereoselecrive Reaction with Organo-Aluminum Reagents and Application to the Synthesis of an Aqqregation Pheromone" Bull.Chem.Soc.Jpn.69. 2095-2105 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] C.Liu: "Regio-and Srereoselective Ring-opening Reaction of 2,3-Epoxy Amines with Organo-aluminum Reagents Leading to 2-Substituted 3-Amino Alcohols" Tetrahedron Lett.37. 6177-6180 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Changqing Liu: "Highly Stereoselective Cationic Cyclization Assisted by a Sulfenyl Group. Scope, Limitation, and Mechanism" J. Org. Chem.61. 494-502 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yukihiko Hashimoto: "Remote a symmetric Induction using Neighboring Group Participation of a Sulfenyl Group" Tetrahedron. 50. 8317-8336 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 橋本幸彦: "隣接基関与を利用する選択的合成反応" 有機合成化学協会誌. 53. 116-121 (1995)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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