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Development of an Efficient "Chiral Technology" Based on the Chiral Coordinating Agent Protocol

Research Project

Project/Area Number 08555221
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 有機工業化学
Research InstitutionTokyo Institute of Technology

Principal Investigator

NAKAI Takeshi  Tokyo Inst.Tech., Fac.Eng., Prof., 工学部, 教授 (90016717)

Co-Investigator(Kenkyū-buntansha) TOMOOKA Katsuhiko  Tokyo Inst.Tech., Fac.Eng., Res., Assoc., 工学部, 助教授 (70207629)
Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1997: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥4,600,000 (Direct Cost: ¥4,600,000)
KeywordsEnantiocontrol / Chiral ligand / Carbanion reaction / Carbanion cyclization / [2,3] -Wittig rearrangement / [1,2] -Wittig rearrangement / 不斉合成 / 不斉リチオ化
Research Abstract

1. Enantioselective S_E2 Reaction of alpha-Methoxy Benzyllithium Generated
via t-BuLi/Chiral Bisoxazoline System In recent years the extemal chiral ligand (ECL) -based asymmetric lithiation/S_E2 reaction has emerged as an efficient strategy for enantioselective C-C bond formations. While most of the successes so far have been made using (-) -sparteine as ECL,the development of other ECL's effective for different reactions is a significant challenge. We have developed the highly enantioselective S_E2 reactions of alpha-methoxy benzyllithium generated via the lithiation (deprotonation) with t-BuLi complexed with the chiral bisoxazoline, (S,S) -Box-i-Pr, as ECL (Lc^*). Of special interest is the reaction with the acetylenic aldehyde which affords the 1,2-diolmonomethyl ether with an extremely high % ee along with a relatively high anti diastereoselectivity.
2. Carbanion Cyclization : Absolute Stereochemistry and Enantiocontrol The carbanion cyclization of 5-alkenyllithiums and their hetero … More analogues has emerged as an efficient method for stereoselective carbocyclization. We have investigated the absolute stereochemistry of the carbanion cyclization and the developed the its enantioselective version.
Absolute Stereochemistry of Carbanion Cyclization : Treatment of enatiomerically defined (R) -alpha-alkenyloxystannanes with n-BuLi at -78゚C was found to afford the cyclization product (S) in high stereoselectivity. Tus the rearrangement is proved to proceeds with completely retention of configuration at the Li-bearing chiral center.
Enantioselective Version of Carbanion Cyclization : Upon treatment with (-) -sparteine / s-BuLi, alkenylcarbamate gave cyclopentane in a high enatioselectivity, along with 6-phenylbicyclo [3.1.0] hexane. More significantly, a similar cyclization of the 4-silyloxy substrate (racemic) was found to afford the silyoxy cyclopentane and the 2-silyloxy bicyclohexane of which the absolute configurations are opposite each other.
3. Enantioselective [2,3] -Wittig Rearrangement Induced by Asymmetric Lithiation with t-Butyllithium/Chiral Bisoxazoline System The [2,3] -Wittig rearrangement, particularly its asymmetric version using enantio-enriched substrates, enjoys wide spread application in many facets of organic synthesis. However, only a few examples have been reported of the enantioselective version that permit direct access to an enantio-enriched product from an achiral substrate. In view of the recent progress in the asymmetric lithiation protocol, we became intriguted by the exploration of enantioselective [2,3] -Wittig variants induced by the ECL-based asymmetric lithiation protocol. Now we have developed the highly enantioselective [2,3] Wittig rearrangement using the chiral bisoxazoline ((S,S) -Box-i-Pr) / t-BuLi system. This is the first example of the utilization of a chiral bisoxazoline as ECL for the enantioselective [2,3] -Wittig rearrangement. Less

Report

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

    (14 results)

All Other

All Publications (14 results)

  • [Publications] 中井 武: "Wittig Rearrangement of α-(Propargyloxy)-alkyllithiums:Periselectivity and Steric Course at the Lithium-bearing Terminus" Synlett. 1045-1049 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 中井 武: "Cyclization of Enantio-Enriched α-(Homoallyloxy)Alkyllithiums:Evidence for Retention of Configuration at The Carbanion Center" Tetrahedron Lett.38. 8939-8942 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 中井 武: "Asymmetric[2,3]-Wittig rearrangement as a general tool for asymmetric synthesis" Pure and Appl.Chem.69. 595-600 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 中井 武: "A Highly Stereocontrolled Conversion of O-Glycosides to C-Glycosides" J.Am.Chem.Soc. 118. 3317-3319 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 中井 武: "[1,2]-Wittig rearrangement:Stereochemical features and syntheticutilities" J.Synth.Org.Chem.Jpn.54. 1000-1008 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Katsuhiko Tomooka, Nobuyuki Komine, Takeshi Nakai: "Wittig Rearrangement of alpha- (Propargyloxy) -alkyllithiums : Periselectivity and Steric Course at the Lithium-bearing Terminus" Synlett. 1997. 1045-1046 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Katsuhiko Tomooka, Nobuyuki Komine, Takeshi Nakai: "Cyclization of Enantio-Enriched alpha- (Homoallyloxy) Alkyllithiums : Evidence for Retention of Configuration at The Carbanion Center" Tetrahedron Lett.38. 8939-8942 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Katsuhiko Tomooka, Hiroshi Yamamoto, Takeshi Nakai: "A Highly Stereocontrolled Conversion of O-Glycosides to C-Glycosides" J.Am.Chem.Soc.118. 3317-3319 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Katsuhiko Tomooka, Takeshi Nakai: "[1,2] -Wittig rearrangement : Stereochemical features and synthetic utilities" J.Synth.Org.Chem.Jpn.54. 1000-1008 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 中井 武 他2名: "Witting Rearrangement of α-(Propargyloxy)-alkyllithiums : Periselectivity and Steric Course at the Lithium-bearing Terminus" Synlett. 1045-1049 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 中井 武 他2名: "Cyclization of Enantio-Enriched α-(Homoallyloxy)Alkyllithiums : Evidence for Retention of Configuration at The Carbanion Center" Tetrahedron Lett.38. 8939-8942 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 中井 武: "A Highly Stereocontrolled Conversion of O-Glycosides to C-Glycosides" J.Am.Chem.Soc.118. 3317-3319 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 中井 武: "[1,2]-Wittig rearrangement: Stereocheical features and synthetic utilities" J.Synth.Org.Chem.Jpn.54. 1000-1008 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 中井 武: "Asymmetric [2,3]-Wittig rearrangement as a general tool for asymmetric synthesis" Pure and Appl.Chem.(in press).

    • Related Report
      1996 Annual Research Report

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

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