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Exploration into Double Nucleophilic Addition Reaction to α, β- Unsaturated Aldimines Promoted by Titanium Tetrahalides

Research Project

Project/Area Number 12650833
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 InstitutionMie University

Principal Investigator

SHIMIZU Makoto  Mie University, Faculty of Engineering, Professor, 工学部, 教授 (30162712)

Project Period (FY) 2000 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2001: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordstitanium tetrahalide / double nucleophilic addition / ketene silyl acetal / α,β-unsaturated aldimine / allylstannene / aluminum chloride / molecular sieves / thiol / 二重球核付加反応 / 共役付加受容体 / α-メタライミン
Research Abstract

In the present study, we found that in the presence of a titanium tetrahalide, ketene silyl acetals underwent 1,4- and subsequently 1,2-addition to α, β-unsaturated aldimine to give doubly alkylated products in good yields. The reaction of a mixture of a ketene silyl acetal and an allyltributylstannane with α,β-unsaturated aldimine gave regio- and chemoselectively 1,4- and 1,2-doubly alkylated product, in which the ketene silyl acetal underwent 1,4-addition while the allyltributylstannane underwent 1,2-addition. Moreover, in the presence of AlCl_3 and MS 4A containing H_2O, ketene silyl acetals underwent 1,4- and then 1,2-addition with α,β-unsaturated imines to give doubly alkylated products in good yields with high diastereomeric excesses. A mixture of thiols and tetraallyltin also underwent 1,4- and 1,2-addition, respectively, with α, β-unsaturated imines with TiCl_4, to give 6-sulfenyl-4-amino-1-alkenes in good yields.

Report

(3 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] M.Shimizu: "N-Alkylation-Coupling Reaction of Imines Promoted by Alkylaluminum Reagents, Leading to a Facile Synthesis of 1,2-Diamines"Tetrahedron Lett.. 42,(15). 2829-2832 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M.Shimizu: "Double nucleophilic addition reaction to α,β-unsaturated aldimines promoted by aluminum chloride and a limited amount of water"Tetrahedron Lett.. 42,(32). 5463-5466 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y.Niwa: "Electrophilic amination with iminomalonate"Tetrahedron Lett.. 42,(32). 5473-5476 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M.Shimizu: "A convenient imino aldol reaction in ethyl alcohol catalyzed by a cation-exchange resin"J. Chem. Soc., Chem. Commun.. (22). 2318-2319 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M.Shimizu: "Retormatsky-type reaction of α-halo ketones promoted by titanium tetraiodide"Tetrahedron. 57,(47). 9591-9595 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M.Shimizu: "Double Nucleophilic Addition of Thiols and Allylstannane to α,β-Unsaturated Aldimines Promoted by Titanium Tetrachloride"Chem Lett.. (1). 46-47 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Shimizu: "N-Alkylation-Coupling Reaction of Imines Promoted by Alkylaluminum Reagents, Leading to a Facile Synthesis of 1,2-Diamines"Tetrahedron Lett.. 42, (15). 2829-2832 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Shimizu: "Double Nucleophilic Addition reaction to α, β-Unsaturated Aldimines Promoted by Aluminum Chloride and a Limited Amount of Water"Tetrahedron Lett.. 42, (32). 5463-5466 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. Niwa: "Electrophilic Amination with Iminomalonate"Tetrahedron Lett.. 42, (32). 5473-5476 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Shimizu: "A Convenient Imino Aldol Reaction in Ethyl Alcohol Catalyzed by a Cation-Exchange Resin"J. Chem. Soc., Chem. Commun.. (22). 2318-2319 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Shimizu: "Reformatsky-Type Reaction of α-Hhalo Ketones Promoted by Titanium Tetraiodide"Tetrahedron. 57, (47). 9591-9595 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Shimizu: "Double Nucleophilic Addition of Thiols and Allylstannane to α,β-Unsaturated Aldimines Promoted by Titanium Tetrachloride"Chem. Lett.. (1). 46-47 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M.Shimizu: "N-Alkylation-Coupling Reaction of Imines Promoted by Alkylaluminum Reagents,Leading to a Facile Synthesis of 1,2-Diamines"Tetrahedron Lett.. 42,(15). 2829-2832 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Shimizu: "Double nucleophilic addition reaction to α,β-unsaturated aldimines promoted by aluminum chloride and a limited amount of water"Tetrahedron Lett.. 42,(32). 5463-5466 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Niwa: "Electrophilic amination with iminomalonate"Tetrahedron Lett.. 42,(32). 5473-5476 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Shimizu: "A convenient imino aldol reaction in ethyl alcohol catalyzed by a cation-exchange resin"J.Chem.Soc.,Chem.Commun.. (22). 2318-2319 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Shimizu: "Reformatsky-type reaction of α-halo ketones promoted by titanium tetraiodide"Tetrahedron. 57,(47). 9591-9595 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Shimizu: "Double Nucleophilic Addition of Thiols and Allylstannane to α,β-Unsaturated Aldimines Promoted by Titanium Tetrachloride"Chem Lett.. (1). 46-47 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Shimizu: "N-Alkylation-Coupling Reaction of Imines Promoted by Alkylaluminum Reagents, Leading to a Facile Synthesis of 1,2-Diamines"Tetrahedron Lett.. (in press). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Hayakawa: "Novel Carbon-Carbon Bond Formation Reaction of Methoxyallene Oxide Promoted by TiI_4."Org.Lett.. 2,(25). 4079-4081 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Shimizu: "Chemoselective Imino Aldol Reaction Promoted by a Cation-Exchange Resin"Synlett. (12). 1828-1830 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Shimizu: "Highly Stereocontrolled Reduction of 1,3-Cyclopentanediones Using Oxazaborolidine-BH_3"Tetrahedron : Asymm.. 11,(19). 3883-3886 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Shimizu: "SChemoselective Deoxygenation of Sulfoxides with Titanium Tetraiodide"Synlett. (10). 1437-1438 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Hayakawa: "Reduction of 1,2-Diketones with Titanium Tetraiodide : A Simple Approach to α-Hydroxy Ketones"Tetrahedron Lett.. 41,(41). 7939-7942 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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