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Organic Synthesis using Silicone as all Organosilicon Reagent

Research Project

Project/Area Number 13650915
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

MORI Atsunori  Tokyo Institute of Technology, Chemical Resources Laboratory, Associate Professor, 資源化学研究所, 助教授 (90210111)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2001: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywordssilicone / organosilicon reagent / cyclic siloxane / polysiloxane / cross-coupling reaction / conjugate addition / tetrabutylammonium fluoride / Mizoroki-Heck-type reaction / 酸化銀
Research Abstract

This research pursued for the purpose of carrying out synthetic organic reactions using silicone as a new class of organosilicon reagent. Silicone bearing an aryl or alkenyl group on the silicon atom was employed for several carbon-carbon bond-forming reactions. Cyclic or polymeric silicone reagent was use for the reaction. In particular, poly (phenylmethylsiloxane), which is a commercially available highly thermo-resistant silicone oil, affected palladium-catalyzed cross-coupling reaction with organic halides to give biaryl derivatives that are potentially available for liquid crystalline organic materials. Alkenylsiloxanes, which was prepared from commercially available PMHS ; poly (methylhydrosiloxane) with alkyne via hydrosilylation, also affected cross-coupling reactions. In these reactions TBAF (tetrabutylammonium fluoride) or Ag_2O served as an effective activator for the reaction. Rhodium-catalyzed reaction of alfa. Beta-unsaturated carbonyl compounds also took place to give the conjugate addition products. On the other hand, the reaction of organosilicon reagents catalyzed by indium complexes brought about the Mizoroki-Heck-type reaction.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (25 results)

All Other

All Publications (25 results)

  • [Publications] A.Mori: "Hydroxorhodium complex-catalyzed carbon-carbon bond forming reactions of silanediols with alfa, beta-unsaturated carbonyl compounds"J. Am. Chem. Soc.. 123・43. 10074-10075 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Fujii: "Rhodium-catalyzed addition of aryl-and alkenylsilanediols to aldehydes"Synlett. ・2. 298-300 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Koike: "Silicone as organosilicon reagent 2. Rhodium-catalyzed conjugate addition of the silicone reagent to alfa, beta-unsaturated carbonyl compounds"Synlett. ・1. 301-303 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Yamamura: "Chirality transfer from silicon to carbons via diastereoselective Simmons-Smith cyclopropanation of chiral alkenlysilanols"Tetrahedron Asymmetry. 13・1. 13-15 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Mori: "[Rh(OH)(cod)]2 (cod=1,5-cyclooctadiene), a highly efficient catalyst for 1,4-hydrosilylation of alfa, beta-unsaturated carbonyl compounds"Synlett. ・7. 1169-1171 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Koike: "Iridium-catalyzed Mizoroki-Heck-type reaction of organosilicon reagents"Angew. Chem., Int. Ed.. 42・1. 89-92 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Mori: "New synthetic reactions using silanols and siloxanes"Latest Frontiers of Organic Synthesis. (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Mori: "Hydroxorhodium complex-catalyzed carbon-carbon bond forming reactions of silanediols with alfa, beta-unsaturated carbonyl compounds."J. Am. Chem. Soc.. 43-123. 10074-10075 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Fujii: "Rhodium-catalyzed addition of aryl-and alkenylsilanediols to aldehydes"Synlett. 2. 298-300 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Koike: "Silicone as organosilicon reagent 2. Rhodium-catalyzed conjugate addition of the silicone reagent to alfa, beta-unsaturated carbonyl compounds"Synlett. 2. 301-303 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Yamamura: "Chirality transfer from silicon to carbons via diastereoselective Simmons-Smith cyclopropanation of chiral alkenylsilanols"Tetrahedron Asymmetry. 1-13. 13-15 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Mori: "[Rh(OH)(cod)]_2 (cod=l,5-cyclooctadiene), a highly efficient catalyst for 1,4-hydrosilylation of alfa, beta-unsaturated carbonyl compounds"Synlett. 7. 1169-1171 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Koike: "Iridium-catalyzed Mizoroki-Heck-type reaction of organosilicon reagents"Angew. Chem., Int. Ed.. 1-42. 89-92 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Mori: "Latest Frontiers of Organic Synthesis"New synthetic reactions using silanols and siloxanes. 19 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Yamamura: "Chirality transfer from silicon to carbons via diastereoselective Simmons-Smith cyclopropanation of chiral alkenylsilanols"Tetrahedron Asymmetry. 13・1. 13-15 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Mori: "[Rh(OH)(cod)]2 (cod=1,5-cyclooctadiene), a highly efficient catalyst for 1,4-hydrosilylation of alfa, beta-unsaturated carbonyl compounds"Synlett. 7. 1169-1171 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Koike: "Iridium-catalyzed Mizoroki-Heck-type reaction of organosilicon reagents"Angew.Chem., Int.Ed.. 42・1. 89-92 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Mori: "Latest Frontiers of Organic Synthesis"New synthetic reactions using silanols and siloxanes. 19 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Mori: "Isomerization of (E)-alkenylsilanes to (Z)-isomers using hydrosilanes and RhI(PPh3)3."Can. J. Chem.. 79・11. 1522-1524 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Mori: "Silicone as a new class of organosilicon reagent for the palladium-catalyzed cross-coupling reaction"Synlett. -・6. 845-847 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Mori: "Hydroxornodium complex-catalyzed carbon-carbon bond forming reactions of silanediols with α,β-unsaturated carbonyl compounds. Mizoroki-Heck type reaction vs conjugate addition."J. Am. Chem. Soc. 123・43. 10774-10775 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Toshinari Fujii: "Rhodium-catalyzed hydroarylation and -alkenylation of alkynes with silanediols. A crucial role of the hydroxy group for the catalytic reaction"Synlett. -・2. 295-297 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Toshinari Fujii: "Rhodium-catalyzed addition of ary- and alkenylsilanediol to aldehyde"Synlett. -・2. 298-300 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tooru Koike: "Silicone as organosilicon reagent2. Rhodium-catalyzed conjugate addition of the silicone reagent to α,β-unsaturated carbonyl compounds"Synlett. -・2. 301-303 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tamejiro Hiyama: "Alkynylsilanes ; Sience of Synthesis"Thieme. 9 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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