Time and Sfcace Control of Reactive Complexes of Carbon and Heavy-Elements

• Project/Area Number: 14078220
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hiroshima University
• Principal Investigator: YAMAMOTO Yohsuke Hiroshima University, Graduate School of Science, Professor, 大学院理学研究科, 教授 (50158317)
• Project Period (FY): 2002 – 2005
• Project Status: Completed (Fiscal Year 2006)
• Budget Amount: ¥24,000,000 (Direct Cost: ¥24,000,000); Fiscal Year 2005: ¥6,400,000 (Direct Cost: ¥6,400,000); Fiscal Year 2004: ¥6,400,000 (Direct Cost: ¥6,400,000); Fiscal Year 2003: ¥5,600,000 (Direct Cost: ¥5,600,000); Fiscal Year 2002: ¥5,600,000 (Direct Cost: ¥5,600,000)
• Keywords: hypervalent / carbon / boron / 高配位 / 硫黄配位子 / X線解析 / 超原子価化合物 / 6配位炭素 / チオキサントン / アレン / ビニル位S_N2反応 / 合成 / 3座配位子 / エックス線解析

Research Abstract

Recently, we reported synthesis and isolation of hypervalent pentacoordinate carbon compounds and hypervalent pentacoordinate boron compounds bearing a rigid anthracene skeleton and a relatively flexible van Koten skeleton. Although the X-ray analysis and density functional calculation of these compounds clearly showed the attractive interaction between the central carbon (boron) and the two coordinating oxygen atoms, these interactions are weak based on the distance and the values from AIM analysis. Thus, we designed a novel tridentate ligand bearing a benzene ring condensed with two seven membered rings in the hope of stronger interaction between the central atom and the coordinating sulfur atoms. We could obtain pentacoordinate carbon compound, but tetracoordinate compounds, where only one of the sulfur atom was coordinating toward the central carbon, were also obtained by changing the substituents on the central carbon atom.

Research Products

• [Journal Article] Application of A Chiral Copper-1,1-Bis{2-[(4S)-tert-butyloxazolinyl]}cyclopropane Catalyst for Asymmetric Cyclopropanation of Styrene (2006)
  • Author(s): Itagaki, M., Yamamoto, Y.
  • Journal Title: Tetrahedron Letters 47 Pages: 523-525
• [Journal Article] Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton-Elucidation of Hyperavalent Interaction Based on X-ray Analysis and DFT Calculation, (2005)
  • Author(s): Yamashita, M, Yamamoto, Y, Akiba, K.-y, Hashizume, D, Iwasaki, F, Takagi, N, Nagase, S
  • Journal Title: J. Am. Chem. Soc. 127 Pages: 4354-4371
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis and Characterization of Stable Hypervakalent Carbon Compounds (10-C-5) Bearing a 2,6-Bis(ρ-substituted phenyloxymethyl)benzene Ligand (2005)
  • Author(s): Akiba, K.-y, Moriyama, Y, Mizozoe, M, Inohara, H, Nishii, T, Yamamoto, Y, Minoura, M, Hashizume, D, Iwasaki, F, Takagi, N, Ishimura, K, Nagase, S
  • Journal Title: J. Am. Chem. Soc. 127 Pages: 5893-5901
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis and Structures of 16 π Octaalkyltetraphenylporphyrins (2005)
  • Author(s): Yamamoto, Y, Yamamoto, A, Furuta, S-y, Horie, M, Kodama, M, Sato W, Akiba, K.-y, Tsuzuki, S, Uchimaru, T, Hashizume, D, Iwasaki, F
  • Journal Title: J. Am. Chem. Soc. 127 Pages: 14540-14541
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton-Elucidation of Hyperavalent Interaction Based on X-ray Analysis and DFT Calculation, (2005)
  • Author(s): Yamashita, M., Yamamoto.Y.: Akiba, K.-y., Hashizume, D., Iwasaki, F., Takagi, N., Nagase, S
  • Journal Title: J. Am. Chem. Soc 127 Pages: 4354-4371
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis and Characterization of Stable Hypervalent Carbon Compounds (10-C-5) Bearing a 2,6-Bis(p-substituted phenyloxymethyl)benzene Ligand (2005)
  • Author(s): Akiba, K.-y., Moriyama, Y., Mizozoe, M., Inohara, H., Nishii, T., Yamamoto.Y.: Minoura, M., Hashizume, D., Iwasaki, F., Takagi, N., Ishimura, K., Nagase, S.
  • Journal Title: J. Am. Chem. Soc 127 Pages: 5893-5901
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis and Structure of 16 n Octaalkyltetraphenylporphyrins (2005)
  • Author(s): Yamamoto.Y.: Yamamoto, A, Furuta, S.-y., Horie, M., Kodama, M., Sato, W., Akiba, K.-y., Tsuzuki, S., Uchimaru, T., Hashizume, D., Iwasaki, F.
  • Journal Title: J. Am. Chem. Soc 127 Pages: 14540-14541
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton-Elucidation of Hyperavalent Interaction Based on X-ray Analysis and DFT Calculation (2005)
  • Author(s): Yamashita, M., Yamamoto, Y., Akiba, K.-y., Hashizume, D., Iwasaki, F., Takagi, N., Nagase, S.
  • Journal Title: Journal of the American Chemical Society 127 Pages: 4354-4371
• [Journal Article] Synthesis and Characterization of Stable Hypervalent Carbon Compounds (10-C-5) Bearing a 2,6-Bis(p-substituted phenyloxymethyl)benzene Ligand (2005)
  • Author(s): Akiba, K.-y., Moriyama, Y., Mizozoe, M., Inohara, H., Nishii, T., Yamamoto, Y., Minoura, M., Hashizume, D., Iwasaki, F., Takagi, N., Ishimura, K., Nagase, S.
  • Journal Title: Journal of the American Chemical Society 127 Pages: 5893-5901
• [Journal Article] Asymmetric Cyclopropanation of 2,5-Dimethyl-2,4-hexadiene by Copper Catalyst Bearing New Bisoxazoline Ligand (2005)
  • Author(s): Itagaki, M., Masumoto, K., Yamamoto, Y.
  • Journal Title: Journal of Organic Chemistry 70 Pages: 3292-3295
• [Journal Article] Evidence for a Transition State Model Compound of In-Plane Vinylic S_N2 Reaction (2005)
  • Author(s): Yamaguchi, T., Yamamoto, Y., Fujiwara, Y., Tanimoto, Y.
  • Journal Title: Organic Letters 7 Pages: 2739-2742
• [Journal Article] Synthesis and Structure of 16 π Octaalkyltetraphenylporphyrins (2005)
  • Author(s): Yamamoto, Y., Yamamoto, A., Furuta, S.-y., Horie, M., Kodama, M., Sato, W., Akiba, K.-y., Tsuzuki, S., Uchimaru, T., Hashizume, D., Iwasaki, F.
  • Journal Title: Journal of the American Chemical Society 127 Pages: 14540-14541
• [Journal Article] Syntheses and Structures of Hypervalent Pentacoordinate Carbon and Boron Compounds Bearing an Anthracene Skeleton-Elucidation of Hyperavalent Interaction Based on X-ray Analysis and DFT Calculation (2005)
  • Author(s): Yamashita, M., Yamamoto, Y., Akiba, K.-y., Hashizume, D., Iwasaki, F., Takagi, N., Nagase.S.
  • Journal Title: J.Am.Chem.Soc. 127 Pages: 4354-4371
• [Journal Article] Synthesis and Characterization of Stable Hypervalent Carbon Compounds (10-C-5) Bearing a 2,6-Bis(p-substituted phenyloxymethyl)benzene Ligand (2005)
  • Author(s): Akiba, K.-y., Moriyama, Y., Mizozoe, M., Inohara, H., Nishii, T., Yamamoto, Y., Minoura, M., Hashizume, D., Iwasaki, F., Tak
  • Journal Title: J.Am.Chem.Soc. 127(印刷中)
• [Journal Article] Asymmetric Cyclopropanation of 2,5-Dimethyl-2,4-hexadiene by Copper Catalyst Bearing New Bisoxazoline Ligand (2005)
  • Author(s): Itagaki, M., Hagiya, K., Kamitamari, M., Masumoto, K., Suenobu
  • Journal Title: J.Org.Chem. 70(印刷中)
• [Journal Article] Highly Efficient Chiral Copper Schiff-base Catalyst for Asymmetric Cyclopropanation of 2,5-Dimethyl-2,4-hexadiene (2004)
  • Author(s): Itagaki, M., Masumoto, K., Yamamoto, Y.
  • Journal Title: Tetrahedron 60 Pages: 7835-7843
• [Journal Article] Syntheses and Reactions of Hexavalent Organotellurium Compounds Bearing Five or Six Tellurium-Carbon Bonds (2004)
  • Author(s): Miyasato, M., Sagami, T., Minoura, M., Yamamoto, Y., Akiba, K.-y.
  • Journal Title: Chem.Eur.J. 10 Pages: 2590-2600
• [Journal Article] First Optically Active Selenurane Oxide : Resolution of C2-Symmetric 3,3,3',3'-Tetramethyl-1-1'-spirobi[3H,2,1]bepzoxaselepole Oxide (2004)
  • Author(s): Drabowicz, J., Luczak, J., Mikolajczyk, M., Yamamoto, Y., Matukawa, S., Akiba, K, -
  • Journal Title: Chirality 16 Pages: 598-601
• [Journal Article] 新規ポルフィリンの合成と構造 (2004)
  • Author(s): 山本 陽介
  • Journal Title: 化学工業 55巻 Pages: 129-132
• [Publications] M.Yamashita, Y.Mita, Y.Yamamoto, K.-y.Akiba: "Synthesis of a New Potential Tridentate Anthracene Ligand Bearing Deprotectable Methoxymethoxy (OMOM) Group at 1,8-Positions ; Attempt to Synthesize Anionic Hypervalent Carbon Compounds"Chem.Eur.J. 9. 3655-3659 (2003)
• [Publications] S.Matsukawa, Y.Yamamoto, K.-y.Akiba: "Reaction of the α-Benzylic Anion of Spiophosphoranes with N,α-Diphenylnitrone : Stereochemistry and Formation of Hexacoordinate Phosphate Bearing 1,2,5-Oxazaphospholidine Ring"Heterocycles. 59. 707-719 (2003)
• [Publications] Z.H.Wang, C.M.Jensen, S.Matsukawa, Y.Yamamoto: "A Structure-activity Relationship for Pincer Palladium(II) Complexes - Influence of Ring-size of Metallacycles on the Activity in Allylic Alkylation"J.Organometal.Chem.. 681. 189-195 (2003)
• [Publications] M.F.Eberhard, S.Matsukawa, Y.Yamamoto, C.M.Jensen: "Novel Unsymmetrical PCP' Pincer Ligands and Their Palladium(II) Complexes"J.Organometal.Chem.. 687. 185-189 (2003)
• [Publications] 山本陽介: "超原子価5配位炭素およびホウ素の合成"化学と工業. 56. 971-972 (2003)
• [Publications] 山本陽介: "新規ポルフィリンの合成と構造"化学工業. 55. 129-132 (2003)
• [Publications] M.Yamashita, K.Kamura, Y.Yamamoto, K.-y.Akiba: "Synthesis of a Novel Potential Tridentate Anthracene Ligand, 1,8-Bis(dimethylamino)-9-bromoanthracene, and its Application as Chelate Ligand for Synthesis of the Corresponding Boron and Palladium Compounds"Chem. Eur. J. 8. 2976-2979 (2002)
• [Publications] M.Nakamoto, S.Kojima, S.Matsukawa, Y.Yamammoto, K.-y.Akiba: "Stereomutation and apicophilicity of diastereomeric spirophosphoranes (10-P-5)"J. Organometal. Chem. 643-644. 441-452 (2002)
• [Publications] S.Matsukawa, S.Kojima, K.Kajiyama, Y.Yamamoto, K.-y.Akiba, S.Re, S.Nagase: "Characteristic Reactions and Properties of C-Apical O-Equatorial (O-cis) Spiropnosphonoranes : Effect of the σ^*P-O Orbital in the Eqnatorial Plane and Isolation of a Hexacoordinate Oxaphosphetane as an Intermediate of the Wittig Type Reaction of 10-P-5 Phosphoranes"J. Am. Chem. Soc. 124. 13154-13170 (2002)
• [Publications] M.Miyasato, M.Minoira, Y.Yamamoto, K.-y.Akiba: "Novel valence expansion reactions using KC_8 : a new route to hexavalent organotellurium compounds from divalent tellurium"Chem. Lett. 288-289 (2002)
• [Publications] S.Matsukawa, K.Kajiyama, S.Kojima, S.-y.Furuta, Y.Yamamoto, K.-y.Akiba: "A New Method for Determining the Difference in Relative Apicophilicity of Carbon Substituents of 10-P-5 Phosphoranes : Disclosure of Solvent Effect on Apicophilicity and Novel Co-crystallization of Two Pseudorotamers in a Single Crystal"Angew. Chem. Int. Ed. 41. 4718-4722 (2002)
• [Publications] M.Yamashita, Y.Mita, Y.Yamamoto, K.-y.Akiba: "Synthesis of a New Potential Tridentate Anthracene Ligand Bearing Deprotectable Methoxymethoxy (OMOM) Group at 1,8-Positions ; Attempt to Synthesize Anionic Hypervalent Carbon Compounds"Chem. Eur. J. 9(in press). (2003)