Research Projects

• Jun. 2008, Jun. 2008, Principal investigator, Competitive research funding
• Apr. 2008, Mar. 2009, Principal investigator, Competitive research funding
• Apr. 2011, Principal investigator, Competitive research funding
• Development of Novel Synthetic Reactions of Oligosilanes using Transition Metal Complexes, 菅野 研一郎, Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (C), 2014, 2017, Principal investigator, Competitive research funding
• Development of Novel Silicon-Silicon Bond Formation Reaction with Transition Metal Complexes, 菅野 研一郎, Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (C), Grant-in-Aid for Scientific Research (C), Gunma University, 2011, 2014, Principal investigator, The transition metal-catalyzed monoreduction of dichlorooligosianes with alkyl Grignard reagents proceeds with high selectivity to afford the corresponding chloro(hydro)oligosilanes in good yields. The satisfactory results were obtained from the reactions with the primary or secondary alkyl Grignard reagents, whereas that with the tertiary alkyl Grignard reagents proceed very sluggishly. Thus obtained chloro(hydro)oligosilanes were successfully introduced a variety of organic substituents by means of the corresponding organolithium or Grignard reagents. These results shows the importance of this method to supply the building blocks for organosilicon clusters., Competitive research funding, 23550044, kaken

  対象リソースIRI
• Unusual Reactions of the Indenyl Ligand on Zirconium and their Applications in Organic Synthesis, 高橋 保, Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (C), Grant-in-Aid for Scientific Research (C), Hokkaido University, 2008, 2011, The indenyl ligand or cyclopentadienyl ligand have been believed as 'inert'. However, in this project, the indenyl ligand of bis(indenyl)zirconacyclopentadienes coupled with diene moiety in the same molecule to give fluorene derivatives in good yields. The size of the substituents on the cyclopentadienyl ligand effects the coupling greatly. The reaction of bis(cyclopentadienyl)zirconacyclopentadienes with titanium chloride gave low yield of the coupling product. However, in the t-butyl cyclopentadienyl ligand issue, the yield was quite high., Competitive research funding, 20550090, kaken

  対象リソースIRI
• Development of Efficient Synthetic Method of Oligoenes via Selective Linear Oligomerization of Alkynes, 菅野 研一郎, Japan Society for the Promotion of Science, Grant-in-Aid for Young Scientists (B), Grant-in-Aid for Young Scientists (B), Hokkaido University, 2008, 2010, Principal investigator, Highly selective synthesis of tri-and tetraene derivatives as single products was achieved via linear oligomerization of different alkynes via a zirconocene and copper-mediated reaction. And, interesting 7-membered-ring formation of a triene derivatives obtained from the above-mentioned reaction was found. These reactions were applicable for variously substituted substrates., Competitive research funding, 20750160, kaken

  対象リソースIRI
• Synthesis and Reactivity of Thermally Stable Zirconocene (II) Species Precursors, 高橋 保, Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (C), Grant-in-Aid for Scientific Research (C), Hokkaido University, 2006, 2008, Reactions of tris (indenyl) zirconium hydride with a variety of alkynes were investigated and evaluated the reactivity of the zirconium complex as zirconocen (II) equivalent. The reaction of tris (indenyl) zirconium hydride with internal alkynes afforded the corresponding zirconacyclopentadienes in high yields. Interestingly, the reaction with terminal arylalkynes produced the2,5-diarylzirconacycles with high selectivity. A reaction of thus obtained bis (indenyl) zirconacyclopentadienes with titanium tetrachloride afforded the corresponding fluorene derivatives via coupling of the diene moiety with the indenyl ligand. This reaction was applicable for alkyl-or aryl-substituted, and bicyclic zirconacyclopentadienes and furnished the substituted fluorenes. Instead of the indenyl ligand, zirconacyclopentadienes having substituted cyclopentadienyl ligands were also applied for the reaction and afforded the corresponding indene derivatives. A comparison of the structural parameters of the zirconacyclopentadienes with the related ones suggested that the coupling reactivity was strongly affected by the distance between the indenyl or cyclopentadienyl ligands and the diene moiety of the zirconacyclopentadienes. The most reactive titanacyclopentadienes have the shortest distance. In addition, the reactivity was increased with increasing the steric bulkiness of the ligand. Titanium tetrachloride played an important role as an oxidant in the reaction., Competitive research funding, 18550089, kaken

  対象リソースIRI
• Development of Novel Synthetic Methods by Cooperative Use of Metalacycles and Late Transition Metal Catalysts, 高橋 保, Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (C), Grant-in-Aid for Scientific Research (C), Hokkaido University, 2004, 2006, In this work, we have developed novel synthetic methods of unsaturated organic compounds by metalacycles and late transition-metal catalysts. With zirconacyclopentadienes and nickel complexes, catalytic synthetic methods of benzene and polycyclic aromatic compounds were found and developed. Moreover, copper-catalyzed synthesis of diallenes from reactions of zirconacyclopentanes with propargyl halides was developed. It was found that a series of nickel-catalyzed cycloaddition reactions of zirconacyclopentadienes with alkenes and alkynes. In the presence of a catalytic amount of nickel(II) chloride bis(triphenylphosphine), a zirconacyclopentadiene reacted with 2 equiv of 1-haloalkyne or allyl halide to afford the corresponding alkynylbenzene or pentasubstituted benzene, respectively. This is striking contrast to the reaction with copper(I) chloride as a catalyst, which produced the corresponding bis(alkynyl)butadiene. It was developed that coupling reactions of zirconacyclopentadienes and 1,2-dihalobenzenens mediated or catalyzed by nickel complexes to afford the corresponding polycyclic compounds. By the precedent method of the coupling reaction which is mediated by copper(I) chloride, the applicable dihaloarenes were limited for the diiodo- or bromoiodoarenes. Substitution of copper(I) to nickel(0) complex, however, raised the reactivity of the zirconacycles toward dibromo- and even dichlorobenzenes. Furthermore, the use of 3-(trifluoromethyl)styrene improved the reaction for the nickel-catalyzed one. That is, in the presense of 10 mol% of Ni(cod)_2 and 20 mol% of PPh_3, the reaction of a zirconacyclopentadiene with 1,2-dihalobenzene afforded the corresponding naphthalene in a good yield. The method was applied for various zirconacyclopentadienes and dihalobenzenes. Reactions of zirconacyclopentanes with propargyl halides in the presence of copper(I) salt were investigated. In the presence of copper(I) chloride, zirconacyclopentanes reacted with two equivalents of a propargyl halide to give bisallenylation products in moderate to high yields. By controlling the amount of CuCl, stepwise allenylation was achieved and a variety of unsymmetrically substituted diallene derivatives were prepared as well., Competitive research funding, 16550088, kaken

  対象リソースIRI
• Development of Synthetic Methods of Organosilicon Compounds by Transition-Metal Complexes, Grants and Funding, 2010, Competitive research funding