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Studies on Remote Asymmetric Induction in Cycloaddition Reactions using Novel Chiral Sulfoxides

Research Project

Project/Area Number 08672434
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionGIFU PHARMACEUTICAL UNIVERSITY

Principal Investigator

ARAI Yoshitsugu  GIFU PHARMACEUTICAL UNIVERSITY,FACULTY OF PHARMCEUTICAL SCIENCES,ASSOCIATE PROFESSOR, 薬学部, 助教授 (10115157)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1997: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1996: ¥1,100,000 (Direct Cost: ¥1,100,000)
Keywordschiral sulfoxide / Diels-Alder reaction / asymmetric reduction / remote asymmetric induction / alpha, beta-unsaturated ketone / Lewis acid / dienophile / diastereoselective / ディールス・アンダー反応 / ヘテロ-ディールス・アルダー反応 / β-(p-トリルスルフィニル)フルフラール / 光学活性チエニルアルコール / 2-(p-トリルスルフィニル)フリル α,β-不飽和ケトン
Research Abstract

Three types of chiral sulfoxides having a 5-membered aromatic heterocycle (furan, thiophene and pyrrole) were synthesized and high levels of diastereoselectivity in addition reactions were observed.
1.Stereoselective reduction
Reduction of chiral 3-(p-tolylsulfinyl)-2-thienyl alkyl (and aryl) keones with diisobutylaluminum hydride afforded the corresponding (S)-thienylcarbinols as the major product, while the similar reduction in the presence of a Lewis acid or lithium tri-sec-butylborohydride (L-Selectride^<<encircledR>>) reduction afforded (R)-alcohols as the major isomer.
2.Stereoselective hetero Diels-Alder reaction
A lanthanide triflate-promoted hetero Diels-Alder reaction of chiral 3-(p-tolylsulfinyl) furaldehyde with Danishefsky's diene proceeded to give the adduct with excellent distereoselectivity.
3.Stereoselective Diels-Alder reaction
2-Futyl and 2-thienyl alpha, beta-enones, bearing a chiral p-tolylsulfinyl group in the heterocycle, served as an efficient dienophile in the Diels-Alder reaction, where the catalytic use of aluminium chloride or a lanthanide triflate effected these cycloadditions with cyclopentadiene affording the endo adduct with high diastereoselectivity, ranging from 91% to 98%. Similarly the enone to which a chiral p-tolylsulfinyl pyrrole moiety was incorporated also underwent the cycloaddition with up to 89% diastereoisomeric excess in the presence of 1 eqiuv. of the Lewis acid. In particular for the Diels-Alder reaction, the auxiliary (i.e.the sulfinyl pyrrole) was recovered after use without any loss of optical purity.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Y.Arai et al.: "Recoverable Chiral Sulfoxide : Asymmetric Diels-Alder Reaction Using Optically Active 1-(2-p-Tolylsulfinyl) pyrrolyl α,β-Unsaturated Ketones as a Dienophile" Chemistry Letters. (2). 145-146 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai et al.: "Highly Stereoselective Aldol Reaction of Chiral 3-(p-Tolylsulfinyl) furfural with Silyl Ketene Acteal Catalyzed by Lanthanide Triflate" Synlett. (12). 1459-1461 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai, A.Suzuki, T.Masuda, Y.Masaki, M.Shiro: "Stereoselective Reduction of Chiral 3-(p-Tolylsulfinyl)-2-thienyl Ketones. A facile Entry to Optically Active Thienylcarbinols" Chem.Pharm.Bull.44. 1765-1769 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai, T.Masuda, Y.Masaki, M.Shiro: "Highly Stereoselective Hetero Diels-Alder Reaction of Chiral 3-(p-Tolylsulfinyl)-2-furaldehyde with Danishefsky's Diene Promoted by a Lanthanoid Lewis Acid" Tetrahedron : Asymmetry. 7. 1199-1204 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai, T.Masuda, Y.Masaki, M.Shiro: "A highly asymmetric, Lewis acid-catalysed Diels-Alder reaction using optically active 2-(3-tolyl-p-sulfinyl) furyl alpha, beta-unsaturated ketones as a dienophile" J.Chem.Soc., Perkin Trans. 1. 759-762 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai, T.Masuda, Y.Masaki: "Recoverable Chiral Sulfoxide : Asymmetric Diels-Alder Reaction Using Optically Active 1-(2-p-Tolylsulfinyl) pyrrolyl alpha, beta-Unsaturated Ketones as a Dienophile" Chem.Lett.145-146 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai, T.Masuda, Y.Masaki: "Highly Stereoselective Aldol Reaction of Chiral 3-(p-Tolylsulfinyl) furfural with Silyl Ketene Acetal Ctalyzed by Lanthanide Triflate" Synlett. 1459-1461 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Arai et al.: "Recoverable Chiral Sulfoxide:Asymmetric Diels-Alder Reaction Using Optically Active 1-(2-p-Tolylsulfinyl)pyrrolyl α,β-Unsaturated Ketones as a Dienophile" Chemistry Letters. (2). 145-146 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Arai et al.: "Highly Stereoselective Aldol Reaction of Chiral 3-(p-Tolylsulfinyl)furfural with Silyl Ketene Acteal Catalyzed by Lanthanide Triflate" Synlett. (12). 1459-1461 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y. Arai: "Stereoselective Reduction of Chiral 3-(p-Tolylsulfinyl)-2-thienyl Ketones. A Facile Entry to Optically Active Thienylcarbinols" Chem. Pharm. Bull.44 (9). 1765-1769 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y. Arai: "Highly Stereoselective Hetero Diels-Alder Reaction of Chiral 3-(p-Tolylsulfinyl)-2-furaldehyde with Danishefsky′s Diene Promoted by a Lanthanoid Lewis Acid" Tetrahedron : Asymmetry. 7 (4). 1199-1204 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y. Arai: "A highly asymmetric, Lewis acid-catalysed Diels-Alder Reaction using optically active 2-(3-tolyl-p-sulfinyl) α, β-unsaturated ketones as a dienophile" J. Chem. Soc. Perkin Trans. 1. 8. 759-762 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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