Control of Properties of Cage-Shaped Metal Complexes

• Project/Area Number: 21350074
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Osaka University
• Principal Investigator: YASUDA Makoto 大阪大学, 大学院・工学研究科, 准教授 (40273601)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000); Fiscal Year 2011: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2010: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2009: ¥12,870,000 (Direct Cost: ¥9,900,000、Indirect Cost: ¥2,970,000)
• Keywords: 立体規制 / ルイス酸 / ホウ素 / ケイ素 / 触媒 / 選択的反応 / ガリウム / 錯体 / ホウ酸

Research Abstract

New type of cage-shaped metal complexes were prepared and applied to Lewis acid chemistry. Our original type of the complex has B(C6H4) 3CH. We modified it to silicon-including type. The complexes with various substituents(electron-withdrawing or donating groups) has been also synthesized. A careful investigation of ligand-dissociation rate on the complexes clarified the tuning factor that is classified into steric and electronic factors. DFT calculation revealed the LUMO energies that contribute to Lewis acid-catalyzed reactions. In fact, some organic transformations using the complexes as a Lewis acid have been employed.

Research Products

• [Journal Article] Lithium Phenolates with A Hexagonal-prismatic Li6O6 Core Isolated via A Cage-shaped Tripodal Ligands System : Crystal Structures and Their Behavior in Solution (2012)
  • Author(s): 中島秀人、安田誠、馬場章夫
  • Journal Title: Dalton Trans. Volume: 41 Issue: 22 Pages: 6602-6606
  • DOI: 10.1039/c2dt30266g
  • Peer Reviewed
• [Journal Article] Recognition of Aromatic Compounds by II Pocket within a Cage-Shaped Borate Catalyst (2012)
  • Author(s): 中島秀人、安田誠、竹田陵祐、馬場章夫
  • Journal Title: Angew. Chem. Volume: 51 Issue: 16 Pages: 3867-3870
  • DOI: 10.1002/anie.201200346
  • Peer Reviewed
• [Journal Article] Cage-Shaped Borate Esters with Tris(2-oxyphenyl) methane or-silane System Frameworks Bearing Multiple Tuning Factors : Geometric and Substituent Effects on their Lewis Acid Properties (2011)
  • Author(s): 安田誠、中島秀人、竹田陵祐、吉岡佐知子、山崎智、千葉貢治、馬場章夫
  • Journal Title: Chem. Eur. J. Volume: 17 Issue: 14 Pages: 3856-3867
  • DOI: 10.1002/chem.201002789
  • Peer Reviewed
• [Journal Article] InCl_3/Me_3SiBr-Catalyzed Direct Coupling between Silyl Ethers and Enol Acetates (2011)
  • Author(s): 大西祥晴・西本能弘・安田誠・馬場章夫
  • Journal Title: Organic Letters Volume: 13 Issue: 10 Pages: 2762-2765
  • DOI: 10.1021/ol200875m
  • Peer Reviewed
• [Journal Article] Indium Tribromide Catalyzed Cross-Claisen Condensation between Carboxylic Acids and Ketene Silyl Acetals Using Alkoxyhydrosilanes (2011)
  • Author(s): 西木能弘
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50 Issue: 37 Pages: 8623-8625
  • DOI: 10.1002/anie.201104140
  • Peer Reviewed
• [Journal Article] Stabilization of Excited State Using Through-Space Interaction between Independent π-Systems Mediated by a peri-Substituted Hydroxy Group in 1-Arylnaphthalenes : Unexpected Blue Emission of 1,3,5-Tris(peri-hydroxynaphthyl)benzene (2011)
  • Author(s): 中島秀人
  • Journal Title: Bull.Chem.Soc.Jpn. Volume: 84 Issue: 10 Pages: 1118-1129
  • DOI: 10.1246/bcsj.20110139
  • NAID: 130004152819
  • Peer Reviewed
• [Journal Article] Synthesis of Cyclopropane-Containing Phosphorus Compounds by Radical Coupling of Butenylindium with Iodophosphorus Compounds (2011)
  • Author(s): 清川謙介
  • Journal Title: Eur.J.Org.Chem. Volume: (印刷中)
  • Peer Reviewed
• [Journal Article] Cage-Shaped Borate Esters with Tris(2-oxyphenyl)methane or -silane System Frameworks Bearing Multiple Tuning Factors : Geometric and Substituent Effects on their Lewis Acid Properties (2011)
  • Author(s): 安田誠
  • Journal Title: Chem.Eur.J. Volume: (印刷中)
  • Peer Reviewed
• [Journal Article] Synthesis and Theoretical Studies of Gallium Complexes Back-Shielded by a Cage-Shaped Framework of Tris(m-oxybenzyl) arene (2010)
  • Author(s): 中島秀人、安田誠、馬場章夫
  • Journal Title: Chem. Commun. Volume: 46 Issue: 26 Pages: 4794-4796
  • DOI: 10.1039/c0cc00253d
  • Peer Reviewed
• [Journal Article] Synthesis and Theoretical Studies of Gallium Complexes Back-Shielded by a Cage-Shaped Framework of Tris(m-oxybenzyl)arene (2010)
  • Author(s): 中島秀人
  • Journal Title: Chem.Commun. Volume: 46 Pages: 4794-4796
  • Peer Reviewed
• [Journal Article] Characterization of the Nucleophilic Allylindium Species Generated from Allyl Bromide and Indium(0) in Aqueous Media (2010)
  • Author(s): 安田誠
  • Journal Title: Eur.J.Org.Chem. Pages: 5359-5363
  • Peer Reviewed
• [Journal Article] Cyclopropylmethylation of Benzylic and Allylic Chlorides with Cyclopropylmethylstannane Catalyzed by Gallium or Indium Halide (2010)
  • Author(s): 清川謙介
  • Journal Title: Org.Lett. Volume: (印刷中)
  • Peer Reviewed
• [Journal Article] a-Alkylation of Carbonyl Compounds by Direct Addition of Alcohols to Enol Acetates (2009)
  • Author(s): 西本能弘
  • Journal Title: Angew.Chem., Int.Ed. Volume: 48 Pages: 9131-9134
  • Peer Reviewed
• [Journal Article] Stereoselective Synthesis of Vicinal Diols by the Stannous Chloride-Mediated Reaction of Unprotected Hydroxyallylic Stannane with Carbonyl Compounds (2009)
  • Author(s): 安田誠
  • Journal Title: Tetrahedron Volume: 65 Pages: 9569-9574
  • Peer Reviewed
• [Journal Article] Isolation and Crystallographic Characterization of Allylindium Species Generated from Allyl Halide and Indium(0) (2009)
  • Author(s): 安田誠
  • Journal Title: Eur.J.Org.Chem. Pages: 5513-5517
  • Peer Reviewed
• [Journal Article] Indium-Catalyzed Coupling Reaction between Silyl Enolates and Alkyl Chlorides or Alkyl Ethers (2009)
  • Author(s): 西本能弘
  • Journal Title: Tetrahedron Volume: 65 Pages: 5462-5471
  • Peer Reviewed
• [Journal Article] Regio- and Stereoselective Generation of Alkenylindium Compounds from Indium Tribromide, Alkynes, and Ketene Silyl Acetals (2009)
  • Author(s): 西本能弘
  • Journal Title: Angew.Chem., Int.Ed. Volume: 48 Pages: 4577-4580
  • Peer Reviewed
• [Presentation] Cage-Shaped Borate Esters with Multiple Tuning Factors : Geometric and Substitutent Effects on their Lewis Acid Properties (2011)
  • Author(s): 安田誠
  • Organizer: The 6th International Conference on Cutting-Edge Organic Chemistry in Asia(ICCEOCA-6) & The 2nd New Phase International Conference on Cutting-Edge Organic Chemistry in Asia(NICCEOCA-2)
  • Place of Presentation: Hong Kong
  • Year and Date: 2011-12-13
• [Presentation] Cage-Shaped Borate Esters with Multiple Tuning Factors : Geometric and Substitutent Effects on their Lewis Acid Properties (2011)
  • Author(s): 安田誠
  • Organizer: The 6th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-6) The 2nd New Phase International Conference on Cutting-Edge Organic Chemistry in Asia (NICCEOCA-2)
  • Place of Presentation: 香港
  • Year and Date: 2011-12-13
• [Presentation] Alkylindium Species for Coupling Reaction with Organic Halides in a Radical Manner (2011)
  • Author(s): 安田誠、馬場章夫
  • Organizer: 5th Pacific Symposium on Radical Chemistry(PSRC-5)
  • Place of Presentation: Wakayama
  • Year and Date: 2011-09-26
• [Presentation] Alkylindium Species for Coupling Reaction with Organic Halides in a Radical Manner (2011)
  • Author(s): 安田誠
  • Organizer: 5th Pacific Symposium on Radical Chemistry (PSRC-5)
  • Place of Presentation: 和歌山
  • Year and Date: 2011-09-26
• [Presentation] カゴ型三座配位子により安定化された六角柱Li6O6コア構造を有するリチウムフェノレートの合成と物性 (2011)
  • Author(s): 中島秀人、安田誠、馬場章夫
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば国際会議場
  • Year and Date: 2011-09-21
• [Presentation] Evaluation of back-shielded gallium complexes by theoretical calculation and their application for a catalytic reaction (2010)
  • Author(s): 中島秀人、安田誠、馬場章夫
  • Organizer: Second International Pacifichem2010
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2010-12-17
• [Presentation] Evaluation of back-shielded gallium complexes by theoretical calculation and their application for a catalytic reaction (2010)
  • Author(s): 中島秀人
  • Organizer: Pacifichem2010
  • Place of Presentation: ハワイ、ホノルル
  • Year and Date: 2010-12-17
• [Presentation] 新規な有機骨格配位子によるルイス酸性制御法 (2010)
  • Author(s): 安田誠
  • Organizer: ヘテロ原子部会平成22年度第2回懇話会
  • Place of Presentation: 大阪
  • Year and Date: 2010-09-24
• [Presentation] Finely Tuned Indium and Boron Lewis Acids for Organic Transformation (2009)
  • Author(s): 安田誠
  • Organizer: 5th Spanish-Portuguese-Japanese Organic Chemistry Symposium
  • Place of Presentation: 大阪大学(吹田)
  • Year and Date: 2009-11-07
• [Presentation] 背面遮蔽型ガリウム錯体の合成と性状制御 (2009)
  • Author(s): 中島秀人
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学(桐生)
  • Year and Date: 2009-09-28
• [Presentation] かご型構造規制を鍵とするホウ素錯体の置換基効果に関する検討 (2009)
  • Author(s): 竹田陵祐
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学(桐生)
  • Year and Date: 2009-09-28
• [Presentation] ヘテロ原子とのスルースペース効果によるビアリール化合物の光物性挙動 (2009)
  • Author(s): 豊島菜穂美
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学(桐生)
  • Year and Date: 2009-09-28
• [Presentation] X線結晶構造解析に基づくアリルインジウム種の構造解明とその反応性 (2009)
  • Author(s): 垪和昌彦
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学(京都)
  • Year and Date: 2009-09-10
• [Remarks] ホームページ
  • URL: http://www.chem.eng.osaka-u.ac.jp/~babaken/