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1996 Fiscal Year Final Research Report Summary

Studies on Structure and Reactivity of Novel Organometallic Reagents

Research Project

Project/Area Number 06403025
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

UTIMOTO Kiitiro  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (90025958)

Co-Investigator(Kenkyū-buntansha) TAKAI Kazuhiko  Okayama University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (00144329)
OSHIMA Koichiro  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (00111922)
Project Period (FY) 1994 – 1996
KeywordsDIMETALLIC REAGENT / STEREOSELECTIVE / CHIRAL ORGANOMETALS / ORGANOZINC COMPOUND / LEAD CATALYST / SILACYCLOBUTANE / ORGANOMANGANESE REAGENT / ORGANOSAMARIUM REAGENT
Research Abstract

Investigators of this group extended the research on generation of new functionalized organometallic reagents and innovation on new synthetic methodologies using the reagents. Research was focused on the generation of multifunctional organometallic reagents, mainly dimetallic reagents, and the development of new highly selective reactions using multi-metal complex system. Main research results obtained within the term of the research project are follows.
1.Studies on gem-Dimetallic Reagents : Generation and Synthetic Applications.
A possibility of direct preparation of gem-dizinc reagents from gem-dihalides was suggested by the use of Pb-catalyzed reaction with Zn. Then, gem-dizinc reagents have been obtained in good yields. Dimetallic reagents thus obtained, RCH (ZnX)_2 where R=H,Me, Me_3Si etc, are useful in organic synthesis ; olefination of carbonyl compounds including ester, and stepwise reaction of electrophiles.
2.New Reactions using Organolanthanoid Reagents.
Generation of chiral a … More lpha-haloalkyl building block from achiral dihalides has been discovered : SmI_2-mediated reaction of 1,1-diiodoethane with chiral aldehydes gave chiral halohydrin in high diastereoselective manner. Chiral 1-iodoethyl reactive block was generated. Ethyl 2-bromoacetate gives ethyl 4-diiodosamario-3-oxo-butanoate selectively in low temperature, whose reaction with ketones and mixed anhydrides afforded hydroxy keto esters and diketo esters, respectively.
3.Organic Synthesis Using Functional Organosilicon Reagents.
Several synthetic reactions using silacyclobutane, dibromomethylsilanes, and acylsilanes have been disclosed. Various new carbon-carbon forming reactions have been studied, including threecomponent coupling of haloacylsilanes, acylsilane, and carbonyl compounds.
4.Use of Manganese in Organic Synthesis.
Some organic reactions using organomanganese and manganese ate-complexes have been studied ; organic synthesis using these manganese species in stereoselective addition to unsaturated bonds and reduction of organic halides were reported. Less

  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] Kiitiro Utimoto: "Ethyl δ-Diiodosamario-β-oxobutanoates, Generation by the Reaction of Ethyl Bromoacetate with Samarium Diiodide and Synthetic Applications" Bull. Soc. Chim. Fr.,. (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Seijiro Matsubara: "Samarium-Medated Highly Stereoselective Reaction of 1,1-Dihaloalkanes with Aldehycles. Generation of Chiral α-Iodoethyl Buildng Block from Achiral 1,1-Diiodoethane" Angew. Chem.109. 631-633 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kenji Okada: "Allylmagnesation and Diallylation of Acetylenic Compounds Catalyzed by Manganese Salts." J. Am. Chem. Soc.110. 6076-6077 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hiroshi Shinokubo: "Facile Syntheses of α-Bromo-α-Silyl Ketones and α-Bromoacylsilanes from tert-Butyldimethylsilyldibromomethane and Carbonyl Compounds" Tetrahedron. 52. 14533-14542 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihiro Horiuchi: "Titanium Tetrachloride-Induced Three-Component Coupling Reaction of α-Haloacylsilane, Allylsilane, and Carbonyl Compound" J. Org. Chem.61. 4483-4486 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko Takai: "Sequential Generation and Utilization of Radical and Anionic Species with a Novel Manganese-Lead Reducing Agent. Three-Component Coupling Reactions of Alkyl Iodides, Electron-Deficient Clefins, and Carbonyl Compounds." J. Org. Chem.61. 7990-7991 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko Takai: "Activation of Manganese Metal by a Catalytic Amount of PbC12 and MeSiC13." Tetrahedron Lett.39. 7049-7052 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kiitiro Utimoto: "Ytterbium Tricyanide : Preparation and Catalytic Activity for the Addition of Cyanotrimethylsilane to Carbonyl Compounds" Appl. Organomet. Chem.9. 413-419 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kiitiro Utimoto: "Diastereoselective 1,4-Addition of Organocopper-Lanthanoid Reagents to α,β-Unsaturated Ketones Containing 1,3-Oxathiane As a Chiral Auxiliary" SYNLETT. 501-502 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Seijiro Matsubara: "Alkylidenation of Ketones by gem-Dibromoalkane, Sml2, and Sm in the Presence of Catalytic Amount of CrCl3" Chem. Lett.259-260 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kohdai Morihata: "Stereoselective Synthesis of 1,3-Diol from β-Hydroxyacylsilane via Rearrangement of Phenyl. Group from Silicon to Carbon." Tetrahedron Lett.36. 5555-5558 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko Takai: "Selective Cyclotrimerization of Acetylenes via Tantalum-Alkyne Complexes" Chem. Lett.851-852 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko Takai: "Formal Hydroallylation of Carbon-Carbon Triple Bonds via Tantalum-Alkyne Complexes. Stereoselective Preparation of 1,4-Dienes" Chem. Lett.315-316 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kiitiro Utimoto, Tsutomu Takai, Toshiki Matsui, Seijiro Matsubara: "Ethyl delta-Diiodosamario-beta-oxobutanoates, Generation by the Reaction of Ethyl Bromoacetate with Samarium Diiodide and Synthetic Applications" Bull.Soc.Chim.Fr.(1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Seijiro Matsubara, Masahito Yoshioka, Kiitiro Utimoto: "Samarium-Mediated Highly Stereoselective Reaction of 1,1-Dihaloalkanes with Aldehydes. Generation of Chiral a Iodoethyl Building Block from Achiral 1,1-Diiodoethane" Angew.Chem.Int.Ed.Engl.37. (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kenji Okada, Koichiro Oshima, and Kiitiro Utimoto: "Allylmagnesation and Diallylation of Acetvlenic Compounds Catalyzed by Manganese Salts." J.Am.Chem.Soc. 118. 6076-6077 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hiroshi Shinokubo, Koichiro Oshima, and Kiitiro Utimoto: "Facile Syntheses of alpha-Bromo-alpha-Silyl Ketones and alpha-Bromoacylsilanes from tert-Butyldimethylsilyldibromomethane and Carbonyl Compounds." Tetrahedron. 52. 14533-14542 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshihiro Horiuchi, Koichiro Oshima, and Kiitiro Utimoto: "Titanium Tetrachloride-Induced Three-Component Coupling Reaction of alpha-Haloacylsilane, Allylsilane, and Carbonyl Compound." J.Org.Chem. 61. 4483-4486 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko Takai, Takashi Ueda, Norihiko Ikeda, and Toshio Moriwake: "Sequential Generation and Utilization of Radical and Anionic Species with a Novel Manganese-Lead Reducing Agent. Three-Component Coupling Reactions of Alkyl Iodides, Electron-Deficient Olefins, and Carbonyl Compounds." J.Org.Chem. 61. 7990-7991 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko Takai, Takashi Ueda, Takaki Hayashi and Toshio Moriwake: "Activation of Manganese Metal by a Catalytic Amount of PbCl_2 and MeSiCl_3." Tetrahedron Lett.39. 7049-7052 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kiitiro Utimoto, Tsutomu Tkai, Yuri Kasuga, Seijiro Matsubara: "Y tterbium Tricyanide : Preparation and Catalytic Activity for the Addition of Cyanotrimethylsilane to Carbonyl Compounds" Appl. Organomet. Chem.9. 413-419 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kiitiro Utimoto, Tomohiro Kodama, Seijiro Matsubara: "Diastereoselective 1,4-Addition of Organocopper-Lanthanoid Reagents to alpha, beta-Unsaturated Ketones Containing 1,3-Oxathiane As a Chiral Auxiliary" SYNLETT. 501-502 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Seijiro Matsubara, Miyuki Horiuchi, Kazuhiko Takai, Kiitiro Utimoto: "lkylidenation of Ketones by gem-Dibromoalkane, Sml_2, and Sm in the Presence of Catalytic Amount of CrCl_3" Chem.Lett.259-260 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kohdai Morihata, Yoshihiro Horiuchi, Masahiko Taniguchi, Koichiro Oshima, and Kiitiro Utimoto: "Stereoselective Synthesis of 1,3-Diol from beta-Hydroxyacylsilane via Rearrangement of Phenyl Group from Silicon to Carbon." Tetrahedron Lett.36. 5555-5558 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko Takai, Masashi Yamada, Kiitiro Utimoto: "Selective Cyclotrimerization of Acetylenes via Tantalum-Alkyne Complexes" Chem.Lett.851-852 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko Takai, Masashi Yamada, Hidetoshi Odaka, Kiitiro Utimoto, Takeshi Fujii, Isao Furukawa: "Formal Hydroallylation of Carbon-Carbon Triple Bonds via Tantalum-Alkyne Complexes. Stereoselective Preparation of 1,4-Dienes" Chem.Lett.315-316 (1995)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-09  

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