Catalytic Transformation Using Tunable Lewis Acidic Species

• Project/Area Number: 19550038
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: YASUDA Makoto Osaka University, 大学院・工学研究科, 准教授 (40273601)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2008: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2007: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: 錯体 / ルイス酸 / ホウ素 / 立体因子 / インジウム / ケイ素 / カップリング / 配位子交換 / ガリウム / ゲルマニウム / 配位子

Research Abstract

金属の性質を緻密に調整する手法の開発を目的とし、金属中心を包みこむ有機骨格を巧みにデザインした「かご型」金属錯体の合成とルイス酸性の緻密な制御を行った。その結果、ある種のかご型ホウ素錯体が触媒として機能することを見いだした。また、アルコールおよびその類縁体の直接置換反応がインジウムとケイ素の複合作用により触媒的に進行することを見いだし、きわめて実用的な合成反応構築の基盤を築くことができた。

Research Products

• [Journal Article] Radical Coupling of Iodocarbonyl Compounds with Butenylindium Generated by Transmetalation between Cyclopropylmethylstannane and Indium Halides (2009)
  • Author(s): 安田 誠
  • Journal Title: Organometallics 28 Pages: 132-139
  • Peer Reviewed
• [Journal Article] Radical Coupling of Iodocarbonyl Compounds with Butenylindium Generated by Transmetalation between Cyclopropylmethylstannane and Indium Halides (2008)
  • Author(s): 安田誠、清川謙介、大崎健司、馬場章夫
  • Journal Title: Organometallics 28 Pages: 132-139
  • Peer Reviewed
• [Journal Article] Direct Coupling of Alcohols with Alkenylsilanes Catalyzed by Indium Trichloride or Bismuth Tribromide (2008)
  • Author(s): 西本能弘、梶岡雅之、齋藤隆博、安田誠、馬場章夫、
  • Journal Title: Chem. Commun. Pages: 6396-6398
  • Peer Reviewed
• [Journal Article] Esters as Acylating Reagent in a Friedel-Crafts Reaction : Indium Tribromide Catalyzed Acylation of Arenes Using Dimethylchlorosilane (2008)
  • Author(s): 西本能弘、Srinivasarao Arulananda Babu、安田誠、馬場章夫
  • Journal Title: J. Org. Chem. 73 Pages: 9465-9468
  • Peer Reviewed
• [Journal Article] Germanium(II)-Mediated Reductive Mannich-Type Reaction of a-Bromoketones to N-Alkylimines (2008)
  • Author(s): 田中真哉、田頭宣雄、千葉貢治、安田誠、馬場章夫
  • Journal Title: Angew. Chem., Int. Ed. 47 Pages: 6620-6623
  • Peer Reviewed
• [Journal Article] Germanium(II)-Mediated Reductive Cross-Aldol Reaction of Bromoaldehydes with Aldehydes : NMR Studies and ab Initio Calculations (2008)
  • Author(s): 田中真哉、田頭宣雄、千葉貢治、安田誠、馬場章夫
  • Journal Title: J. Org. Chem. 73 Pages: 6312-6320
  • Peer Reviewed
• [Journal Article] Direct Chlorination of Alcohols with Chlorodimethylsilane Catalyzed by a Gallium Trichloride/Tartrate System under Neutral Conditions (2008)
  • Author(s): 安田誠、清水健司、山崎智、馬場章夫
  • Journal Title: Org. Biomol. Chem. 6 Pages: 2790-2795
  • Peer Reviewed
• [Journal Article] Fine-Tuning of Boron Complexes with Cage-Shaped Ligand Geometry : Rational Design of Triphenolic Ligand as a Template for Structure Control (2008)
  • Author(s): 安田誠、吉岡佐知子、中島秀人、千葉貢司、馬場章夫
  • Journal Title: Org. Lett. 10 Pages: 929-932
  • Peer Reviewed
• [Journal Article] Direct Coupling of Alcohols with Alkenylsilanes Catalyzed by Indium Trichloride or Bismuth Tribromide (2008)
  • Author(s): 西本能弘
  • Journal Title: Chem. Commun. Pages: 6396-6398
  • Peer Reviewed
• [Journal Article] Esters as Acylating Reagent in a Friedel-Crafts Reaction : Indium Tribromide Catalyzed Acylation of Arenes Using Dimethylchlorosilane (2008)
  • Author(s): 西本能弘
  • Journal Title: J. Org. Chem. 73 Pages: 9465-9468
  • Peer Reviewed
• [Journal Article] Germanium(II)-Mediated Reductive Mannich-Type Reaction of α-Bromok etones to N-Alkylimines (2008)
  • Author(s): 田中真哉
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 6620-6623
  • Peer Reviewed
• [Journal Article] Germanium(II)-Mediated Reductive Cross-Aldol Reaction of Bromoaldehy des with Aldehydes : NMR Studies and ab Initio Calculations (2008)
  • Author(s): 田中真哉
  • Journal Title: J. Org. Chem. 73 Pages: 6312-6320
  • Peer Reviewed
• [Journal Article] Direct Chlorination of Alcohols with Chlorodimethylsilane Catalyzed by a Gallium Trichloride/Tartrate System under Neutral Conditions (2008)
  • Author(s): 安田 誠
  • Journal Title: Org. Biomol. Chem. 6 Pages: 2790-2795
  • Peer Reviewed
• [Journal Article] Fine-Tuning of Boron Complexes with Cage-Shaped Ligand Geometry: Rational Design of Triphenolic Ligand as a Template for Structure Control (2008)
  • Author(s): 安田 誠
  • Journal Title: Org. Lett. 10 Pages: 929-932
  • Peer Reviewed
• [Journal Article] Coupling Reaction of Alkyl Chlorides with Silyl Enolates Catalyzed by Indium Trihalide (2007)
  • Author(s): 西本能弘、安田誠、馬場章夫
  • Journal Title: Org. Lett. 9 Pages: 4931-4934
  • Peer Reviewed
• [Journal Article] InCl_3/I_2-Catalyzed Cross-Coupling of Alkyl Trimethylsilyl Ethers and Allylsilanes via an in Situ Derived Combined Lewis Acid of InCl_3 and Me_3SiI (2007)
  • Author(s): 齋藤隆博、西本能弘、安田誠、馬場章夫
  • Journal Title: J. Org. Chem. 72 Pages: 8588-8590
  • Peer Reviewed
• [Journal Article] InCl_3/I_2-Catalyzed Cross-Coupling of Alkyl Trimethylsilyl Ethers and Allylsilanesvia an in Situ Derived Combined Lewis Acid of InCl_3 and Me_3SiI (2007)
  • Author(s): 齋藤隆博
  • Journal Title: J. Org. Chem. 72 Pages: 8588-8590
  • Peer Reviewed
• [Journal Article] Coupling Reaction of Alkyl Chlorides with Silyl Enolates Catalyzed by Indium Trihalide (2007)
  • Author(s): 西本能弘
  • Journal Title: Org. Lett. 9 Pages: 4931-4934
  • Peer Reviewed
• [Journal Article] Diastereoselective Producticn of Homoallylic Alcohols Bearing Quaternary Centers from γ-Substituted Allylic Indiums and Ketones (2007)
  • Author(s): Srinivasarao Arulananda Babu
  • Journal Title: J. Org. Chem. 72 Pages: 10264-10267
  • Peer Reviewed
• [Journal Article] Highly Stereoselective Synthesis of Vicinal Diols by Stannous Chloride-Mediated Addition of Hydroxyallylic Stannanes to Aldehydes
  • Author(s): 安田 誠
  • Journal Title: Tetrahedron Lett. (印刷中)
  • Peer Reviewed
• [Presentation] かご型ホウ素錯体による系統的なルイス酸性制御 (2008)
  • Author(s): 中島秀人
  • Organizer: 第19回基礎有機化学討論会
  • Place of Presentation: 大阪大学
  • Year and Date: 2008-10-03
• [Presentation] 臭化インジウムとジメチルクロロシランを用いたエステルからのFriedel-Craft_8アシル化反応 (2008)
  • Author(s): 西本能弘
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-30
• [Presentation] インジウムとの金属交換を利用したシクロプロピルメチルスズとハロカルボニル化合物のカップリング反応 (2008)
  • Author(s): 清川謙介
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-30
• [Presentation] マイクロ波効果を利用した有機合成 (2008)
  • Author(s): 安田 誠
  • Organizer: 合成工学シンポジウム 東京工業大学G-COEプログラム
  • Place of Presentation: 東京工業大学
  • Year and Date: 2008-07-11
• [Presentation] インジウムを用いた有機塩化物とシリルエノラートのカップリング反応 (2007)
  • Author(s): 安田誠
  • Organizer: 第54回有機金属討論会
  • Place of Presentation: 広島大学
  • Year and Date: 2007-10-27
• [Presentation] インジウム触媒を用いた有機塩化物とシリルエノラートのカプリング反応 (2007)
  • Author(s): 安田 誠
  • Organizer: 第54回有機金属化学討論会
  • Place of Presentation: 広島大学
  • Year and Date: 2007-10-27
• [Presentation] Synthetic Application of Indium Hydride (2007)
  • Author(s): 安田誠
  • Organizer: IUPAC 3rd International Symposium on Novel Materials and Synthesis (NMS-III) & 17th International Symposium on Fine Chemistry and Functional Polymers (FCFP-XVII)
  • Place of Presentation: Shanghai, China
  • Year and Date: 2007-10-18
• [Presentation] Structure-Controlled Metal Complexes for Creation of New Catalyst (2007)
  • Author(s): 安田誠
  • Organizer: Second International Symposium on Atomic Technologies
  • Place of Presentation: 淡路、兵庫
  • Year and Date: 2007-10-01
• [Presentation] Structure-Controlled Metal Complexes for Creation of New Catalyst (2007)
  • Author(s): 安田 誠
  • Organizer: Second International Symposium on Atomic Technologies
  • Place of Presentation: Awaji, Hyogo
  • Year and Date: 2007-10-01
• [Remarks]
  • URL: http://www.chem.eng.osaka-u.ac.jp/~babaken/