INTRODUCTION OF BORYL OR SILYL GROUPS VIA AROMATIC OR ALIPHATIC CARBON-HYDROGEN BOND ACTIVATION

• Project/Area Number: 17065001
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: ISHIYAMA Tatsuo Hokkaido University, 大学院工学研究科, 准教授 (00232348)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥16,400,000 (Direct Cost: ¥16,400,000); Fiscal Year 2008: ¥4,700,000 (Direct Cost: ¥4,700,000); Fiscal Year 2007: ¥4,700,000 (Direct Cost: ¥4,700,000); Fiscal Year 2006: ¥4,700,000 (Direct Cost: ¥4,700,000); Fiscal Year 2005: ¥2,300,000 (Direct Cost: ¥2,300,000)
• Keywords: 有機ホウ素化合物 / 有機ケイ素化合物 / 炭素-水素結合活性化 / ホウ素化 / ケイ素化 / 遷移金属触媒 / アリール型ホウ素化合物 / オルト位ホウ素化 / イリジウム触媒 / 安息香酸エステル / ジボロン / ビニル型ホウ素化合物 / 環状ビニルエーテル / ベンジル型ホウ素化合物 / アルキルアレーン / パラジウム触媒 / アリール型ケイ素化合物 / 芳香族炭素-水素結合活性化 / アレーン / ヘテロアレーン / クロスカップリング / 1,4-付加 / 非対称ビアリール

Research Abstract

入手容易で安価な芳香族並びに脂肪族化合物の炭素-水素結合活性化を機軸とするジボロンやヒドロボランあるいはジシランやヒドロシランによる直接的なホウ素化反応およびケイ素化反応が、イリジウムなどの適当な遷移金属錯体を触媒として用いることにより進行することを明らかにした。これらの反応は、有機合成中間体、生理活性物質あるいは機能性分子として注目されている有機ホウ素およびケイ素化合物の経済的で環境調和型かつ効率的な合成法である。

Research Products

• [Journal Article] Vinylic C-H borylation of cyclic vinyl ethers with bis(pinacolato)diboron catalyzed by an iridium(I)-dtbpy complex (2008)
  • Author(s): Takao Kikuchi, Jun Takagi, Hironori Isou, Tatsuo Ishiyama and Norio Miyaura
  • Journal Title: Chem. Asian J 3 Pages: 2082-2090
  • Peer Reviewed
• [Journal Article] Iridium-catalyzed vinylic C-H borylation of cyclic vinyl ethers by bis(pinacolato)diboron (2008)
  • Author(s): Takao Kikuchi, Jun Takagi, Tatsuo Ishiyama and Norio Miyaura
  • Journal Title: Chem. Lett 37 Pages: 664-665
  • NAID: 10021081657
  • Peer Reviewed
• [Journal Article] Practical synthesis of pinacolborane for one-pot synthesis of unsymmetrical biaryls via aromatic C-H borylation-cross-coupling sequence (2008)
  • Author(s): Takao Kikuchi, Yusuke Nobuta, Junko Umeda, Yasunori Yamamoto, Tatsuo Ishiyama and Norio Miyaura
  • Journal Title: Tetrahedron 64 Pages: 4967-4971
  • NAID: 120005438276
  • Peer Reviewed
• [Journal Article] Practical synthesis of pinacolborane for one-pot synthesis of unsymmetrical biaryls via aromatic C-H borylation-cross-coupling sequence (2008)
  • Author(s): Takao Kikuchi
  • Journal Title: Tetrahedron 64 Pages: 4967-4971
  • Peer Reviewed
• [Journal Article] Iridium-catalyzed vidylic C-Hborylation of cyclic vinyl ethers by bis(pinacolato) diboron (2008)
  • Author(s): Takao Kikuchi
  • Journal Title: Chem. Lett 37 Pages: 664-665
  • Peer Reviewed
• [Journal Article] Vinylic C-H borylation of cyclic vinyl ethers with bis(pinacolato) diboron catalyzed by an iridium(I)-dtbpy complex (2008)
  • Author(s): Takao Kikuchi
  • Journal Title: Chem. Asian J 3 Pages: 2082-2090
  • Peer Reviewed
• [Journal Article] Improvements of efficiency and regioselectivity in the iridium(I)-catalyzed aromatic C-H silylation of arenes with fluorodisilanes (2006)
  • Author(s): Takeaki Saiki, Yukihiro Nishio, Tatsuo Ishiyama and Norio Miyaura
  • Journal Title: Organometallics 25 Pages: 6068-6073
  • Peer Reviewed
• [Journal Article] Iridium-catalyzed borylation of arenes and heteroarenes via C-H activation (2006)
  • Author(s): Tatsuo Ishiyama and Norio Miyaura
  • Journal Title: Pure Appl. Chem 78 Pages: 1369-1375
  • NAID: 120005438275
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Borylation of Arenes and Heteroarenes via C-H Activation (2006)
  • Author(s): Tatsuo Ishiyama
  • Journal Title: Pure Appl. Chem. 78・7 Pages: 1369-1375
  • NAID: 120005438275
• [Journal Article] Improvements of Efficiency and Regioselectivity in the Iridium(I)-Catalyzed Aromatic C-H Silylation of Arenes with Fluorodisilanes (2006)
  • Author(s): Takeaki Saiki
  • Journal Title: Organometalics 25・26 Pages: 6068-6073
• [Journal Article] Hartwig、Mechanism of the mild functionalization of arenes by diboron reagents catalyzed by iridium complexes. Intermediacy and chemistry of bipyridine-ligated iridium trisboryl complexes (2005)
  • Author(s): Timothy. M. Boller, Jaclyn M. Murphy, Marco Hapke, Tatsuo Ishiyama, Norio Miyaura and John F
  • Journal Title: J. Am. Chem. Soc 127 Pages: 14263-14278
  • Peer Reviewed
• [Journal Article] Regioselective aromatic C-H silylation of five-membered heteroarenes with fluorodisilanes catalyzed by iridium(I) complexes (2005)
  • Author(s): Tatsuo Ishiyama, Kazuaki Sato, Yukihiro Nishio, Takeaki Saiki and Norio Miyaura
  • Journal Title: Chem. Commun Pages: 5065-5067
  • NAID: 120005438282
  • Peer Reviewed
• [Journal Article] Iridium-catalyzed C-H borylation of arenes and heteroarenes : 1-chloro-3-iodo-5-(4,4,5,5-tetrameth yl-1,3,2-dioxaborolan-2-yl)benzene and 2-(4,4,5,5,-tetramethyl-1,3,2-dioxab orolan-2-yl)indole (2005)
  • Author(s): Tatsuo Ishiyama, Jun Takagi, Yusuke Nobuta and Norio Miyaura
  • Journal Title: Org. Synth 82 Pages: 126-133
  • NAID: 120005438250
  • Peer Reviewed
• [Journal Article] Transition metal-catalyzed direct borylation and silylation based on C-H activation (2005)
  • Author(s): Tatsuo Ishiyama
  • Journal Title: J. Syth. Org. Chem., Jpn 63 Pages: 440-452
  • NAID: 10015726776
  • Peer Reviewed
• [Journal Article] Transition Metal-Catalyzed Direct Borylation and Silylation Based on C-H Activation (2005)
  • Author(s): Tatsuo Ishiyama
  • Journal Title: J.Synth.Org.Chem., Jpn. 63・5 Pages: 440-452
  • NAID: 10015726776
• [Journal Article] Regioselective Aromatic C-H Silylation of Five-Membered Heteroarenes with Fluorodisilanes Catalyzed by Iridium(I) Complexes (2005)
  • Author(s): Tatsuo Ishiyama
  • Journal Title: Chem.Commun. -・40 Pages: 5065-5067
  • NAID: 120005438282
• [Journal Article] Mechanism of the Mild Functionalization of Arenes by Diboron Reagents Catalyzed by Iridium Complexes. Intermediacy and Chemistry of Bipyridine-Ligated Iridium Trisboryl Complexes (2005)
  • Author(s): Timothy M.Boller
  • Journal Title: J.Am.Chem.Soc. 127・41 Pages: 14263-14278
• [Journal Article] Iridium-Catalyzed C-H Borylation of Arenes and Heteroarenes : 1-Chloro-3-iodo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene and 2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)indole (2005)
  • Author(s): Tatsuo Ishiyama
  • Journal Title: Org.Synth. 82・- Pages: 126-133
  • NAID: 120005438250
• [Presentation] イリジウム触媒を用いたフルオロジシランによるビニル位C-H ケイ素化反応 (2009)
  • Author(s): 高田瑠美,岸田恵美,石山竜生,宮浦憲夫
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学、船橋
  • Year and Date: 2009-03-30
• [Presentation] イリジウム触媒を用いたフルオロジシランによるビニル位C-Hケイ素化反応 (2009)
  • Author(s): 高田留美
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学(船橋)
  • Year and Date: 2009-03-30
• [Presentation] Ortho-Borylation of Benzoate Esters with Diborons Catalyzed by Iridium Complexes (2008)
  • Author(s): Takao Kikuchi, Hironori Isou, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: 55th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Osaka Prefecture University Osaka
  • Year and Date: 2008-09-29
• [Presentation] Ortho-Borylation of Benzoate Esters with Diborons Catalyzed by Iridium Complexes (2008)
  • Author(s): Takao Kikuchi
  • Organizer: 55th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Osaka Prefecture University Osaka, Japan
  • Year and Date: 2008-09-29
• [Presentation] Iridium-Catalyzed ortho-Borylation of Benzoate Esters by Diborons (2008)
  • Author(s): Tatsuo Ishiyama, Hironori Isou, Takao Kikuchi and Norio Miyaura
  • Organizer: XIII International Conference on Boron Chemistry
  • Place of Presentation: Palau d'Esports I Congressos、Platja d'Aro
  • Year and Date: 2008-09-23
• [Presentation] Iridium-Catalyzed ortho-Borylation of Benzoate Esters by Diborons (2008)
  • Author(s): Tatsuo Ishiyama
  • Organizer: XIII International Conference on Boron Chemistry
  • Place of Presentation: Palau d'Esports i Congressos Platja d'Aro, Spain
  • Year and Date: 2008-09-23
• [Presentation] Iridium-Catalyzed Borylation of Cyclic Vinyl Ethers via Vinylic C-H Activation (2008)
  • Author(s): Takao Kikuchi
  • Organizer: Catalysis as the Basis for the Innovation in Material Science
  • Place of Presentation: Hokkaido University Sapporo,Japan)
  • Year and Date: 2008-06-16
• [Presentation] Iridium-Catalyzed Aromatic C-H Silylation by 1-Hydrosilatrane (2008)
  • Author(s): Tatsuo Ishiyama and Norio Miyaura
  • Organizer: Third International Conference on Advanced Organic Synthesis directed toward the Ultimate Efficiency and Practicability
  • Place of Presentation: Otsu Prince Hotel、Otsu
  • Year and Date: 2008-05-27
• [Presentation] Iridium-Catalyzed Aromatic C-H Silylation by 1-Hydrosilatrane (2008)
  • Author(s): Tatsuo Ishiyama
  • Organizer: Third International Conference on Advanced Organic Synthesis directed toward the Ultimate Efficiency and Practicability
  • Place of Presentation: Otsu Prince Hotel Otsu, Japan
  • Year and Date: 2008-05-27
• [Presentation] イリジウム触媒を用いたジボロンによる安息香酸エステルのオルト位ホウ素化反応 (2008)
  • Author(s): 異相宏典,菊地貴夫,石山竜生,宮浦憲夫
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学、東京
  • Year and Date: 2008-03-30
• [Presentation] イリジウム触媒を用いたジボロンによる安息香酸エステルのオルト位ホウ素化反応 (2008)
  • Author(s): 菊地 貴夫
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学(東京)
  • Year and Date: 2008-03-30
• [Presentation] Iridium-Catalyzed Borylation of Cyclic Vinyl Ethers via Vinylic C-H Activation (2008)
  • Author(s): Takao Kikuchi, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: Catalysis as the Basis for the Innvation in Materials Science
  • Place of Presentation: Hokkaido University、Sapporo
  • Year and Date: 2008-01-16
• [Presentation] Iridium Catalyzed Aromatic C-H Borylation (2008)
  • Author(s): Tatsuo Ishiyama
  • Organizer: 1st Japan-Singapore Bilateral Symposium on Catalysis
  • Place of Presentation: National University of Singapore、 Singapore
  • Year and Date: 2008-01-08
• [Presentation] Iridium-Catalyzed Direct Silylation of Heteroarenes by 1-Hydrosilatrane (2007)
  • Author(s): Rumi Takata, Emi Kishida, Takeaki Saiki, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: 54th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Hiroshima University
  • Year and Date: 2007-10-27
• [Presentation] Iridium-Catalyzed Direct Silylation of Heteroarenes by 1-Hydrosilatrane (2007)
  • Author(s): Rumi Takata
  • Organizer: 54th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Hiroshima University (Higashihiroshima, Japan)
  • Year and Date: 2007-10-27
• [Presentation] Iridium-Catalyzed Borylation of Cyclic Vinyl Ethers via Vinylic C-H Activation (2007)
  • Author(s): Takao Kikuchi, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: 14th IUPAC International Symposium on Organometallic Chemistry diorected towards Organic Synthesis
  • Place of Presentation: Nara Centennial Hall、Nara
  • Year and Date: 2007-08-03
• [Presentation] Iridium-Catalyzed Borylation of Cyclic Vinyl Ethers via Vinylic C-H Activation (2007)
  • Author(s): Takao Kikuchi
  • Organizer: 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: Nara Centennial Hall(Nara, Japan)
  • Year and Date: 2007-08-03
• [Presentation] イリジウム触媒を用いた 1-ヒドロシラトランによる芳香族C-H 結合の直接ケイ素化反応 (2007)
  • Author(s): 高田瑠美,岸田恵美,斎木丈章,石山竜生,宮浦憲夫
  • Organizer: 日本化学会北海道支部2007年夏季研究発表会
  • Place of Presentation: 旭川工業高等専門学校、旭川
  • Year and Date: 2007-07-21
• [Presentation] イリジウム触媒を用いた1-ヒドロシラトランによる芳香族C-H結合の直接ケイ素化 (2007)
  • Author(s): 高田 瑠美
  • Organizer: 日本化学会北海道支部2007年夏季研究発表会
  • Place of Presentation: 旭川工業高等専門学校(旭川)
  • Year and Date: 2007-07-21
• [Presentation] Iridium-Catalyzed C-H Silylation of Heteroarenes by Fluorodisilanes (2007)
  • Author(s): Tatsuo Ishiyama and Norio Miyaura
  • Organizer: International Conference on Asymmetric Organocatalysis
  • Place of Presentation: Otsu Prince Hotel、Otsu
  • Year and Date: 2007-05-29
• [Presentation] Iridium-Catalyzed C-H Silylation of Heteroarenes by Fluorodisilanes (2007)
  • Author(s): Tatsuo Ishiyama
  • Organizer: International Conference on Asymmetric Organocatalysis
  • Place of Presentation: Otsu Prince Hotel(Otsu, Japan)
  • Year and Date: 2007-05-29
• [Presentation] イリジウム触媒を用いるアレーンのC-H ホウ素化とケイ素化 (2007)
  • Author(s): 石山竜生
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学千里山キャンパス、吹田
  • Year and Date: 2007-03-27
• [Presentation] イリジウム触媒を用いた 1-ヒドロシラトランによるヘテロアレーン類の直接ケイ素化反応 (2007)
  • Author(s): 岸田恵美,高田瑠美,斎木丈章,石山竜生,宮浦憲夫
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学千里山キャンパス、吹田
  • Year and Date: 2007-03-25
• [Presentation] イリジウム触媒を用いた環状ビニルエーテル類の直接ホウ素化反応 (2006)
  • Author(s): 菊地貴夫,石山竜生,宮浦憲夫
  • Organizer: 第18回万有札幌シンポジウム
  • Place of Presentation: 北海道厚生年金会館、札幌
  • Year and Date: 2006-07-08
• [Presentation] イリジウム触媒を用いた1-ヒドロシラトランによるアレーン類の脱水素-ケイ素化反応 (2006)
  • Author(s): 斎木丈章,岸田恵美,石山竜生,宮浦憲夫
  • Organizer: 日本化学会第86春季年会
  • Place of Presentation: 日本大学船橋キャンパス、船橋
  • Year and Date: 2006-03-29
• [Presentation] ビニル位C-H ホウ素化-クロスカップリング法によるC-アリールグリコシド類の簡便合成 (2006)
  • Author(s): 菊地貴夫,石山竜生,宮浦憲夫
  • Organizer: 日本化学会第86春季年会
  • Place of Presentation: 日本大学船橋キャンパス、船橋
  • Year and Date: 2006-03-29
• [Presentation] Aromatic C-H Silylation of Arenes with Fluorodisilanes Catalyzed by Iridiumu Complexes (2006)
  • Author(s): Tatsuo Ishiyama and Norio Miyaura
  • Organizer: 1st International Conference on Cutting-Edge Organic Chemistry in Asia
  • Place of Presentation: Tiruru,Naha
• [Presentation] イリジウム触媒を用いたピナコールボランによる環状ビニルエーテルの脱水素-ホウ素化反応 (2006)
  • Author(s): 異相宏典,菊地貴夫,石山竜生,宮浦憲夫
  • Organizer: 第23回有機合成セミナー
  • Place of Presentation: グリーンピア大沼、大沼
• [Presentation] Direct Silylation of Arenes with 1-Hydrosilatrane Catalyzed by Iridium Complexes (2006)
  • Author(s): Emi Kishida, Takeaki Saiki, Tatsuo Ishiyama, and Norio Miyaura
  • Organizer: 53rd Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Osaka City University、Osaka
• [Presentation] Vinylic C-H Borylation of Cyclic Vinyl Ethers with Bis(pinacolato)diboron Catalyzed by Iridium Complexes (2006)
  • Author(s): Takao Kikuchi, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: XXII International Conference on Organometallic Chemistry
  • Place of Presentation: Zaragoza University、Zaragoza、Spain
• [Presentation] Iridium-Catalyzed Vinylic C-H Borylation of Cyclic Vinyl Ethers by Bis(pinacolato)diboron (2005)
  • Author(s): Takao Kikuchi, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: 52nd Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Doshisha University、Kyoto
• [Presentation] Improvements of Efficiency and Regioselectivity in the Iridium(I)-Catalyzed Aromatic C-H Silylation of Arenes with Fluorodisilanes (2005)
  • Author(s): Takeaki Saiki, Yukihiro Nishio, Tatsuo Ishiyama and Norio Miyaura
  • Organizer: 52nd Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: Doshisha University、Kyoto
• [Presentation] Dehydrogenative Borylation of Aromatic Compounds with Pinacolborane Catalyzed by Iridium(I) Complexes at Room Temperature (2005)
  • Author(s): Tatsuo Ishiyama, John F. Hartwig and Norio Miyaura
  • Organizer: 12th International Conference on Boron Chemistry
  • Place of Presentation: Aendai International Center、Sendai
• [Book] 化学ディビジョンレポート「有機化学ディビジョン・炭素骨格合成・C-C結合生成・有機ホウ素化合物を用いる反応」 (2007)
  • Author(s): 石山竜生
  • Total Pages: 3
  • Publisher: 社団法人日本化学会
• [Book] 化学ディビジョンレポート「有機化学ディビジョン・遷移金属錯体を用いる有機合成・9族元素化学・Ir」 (2007)
  • Author(s): 石山竜生
  • Total Pages: 3
  • Publisher: 社団法人日本化学会
• [Book] Handbook of C-H Transformations (2005)
  • Author(s): Tatsuo Ishiyama and Norio Miyaura
  • Publisher: Wiley-VCH
• [Book] Boronic Acids (2005)
  • Author(s): Tatsuo Ishiyama and Norio Miyaura
  • Publisher: Wiley-VCH
• [Book] Handbook of C-H Transformations, Application in Organic Synthesis Volume l (2005)
  • Author(s): Tatsuo Ishiyama
  • Total Pages: 6
  • Publisher: Wiley-VCH
• [Remarks]
  • URL: http://om-mc.eng.hokudai.ac.jp/indexj.html
• [Remarks]
  • URL: http://om-mc.eng.hokudal.ac.jp/indexj.html
• [Patent(Industrial Property Rights)] 有機ケイ素化合物の製造方法 (2008)
  • Inventor(s): 宮浦憲夫,石山竜生,斎木丈章
  • Industrial Property Rights Holder: 東レ・ダウコーニング株式会社
  • Filing Date: 2008-03-27
• [Patent(Industrial Property Rights)] 有機ケイ素化合物の製造方法 (2008)
  • Inventor(s): 宮浦憲夫
  • Industrial Property Rights Holder: 東レ・ダウコーニング株式会社
  • Acquisition Date: 2008-03-27
• [Patent(Industrial Property Rights)] オルガノシラン類の製造方法 (2003)
  • Inventor(s): 宮浦憲夫
  • Industrial Property Rights Holder: 東レ・ダウコーニング・シリコーン株式会社
  • Filing Date: 2003-09-03
  • Acquisition Date: 2005-03-24