Functionalization of Unactivated Bonds by Cooperative Metal Catalysis

• Project Area: Molecule Activation Directed toward Straightforward Synthesis
• Project/Area Number: 22105003
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: NAKAO Yoshiaki 京都大学, 工学(系)研究科(研究院), 教授 (60346088)
• Co-Investigator(Renkei-kenkyūsha): SEMBA Kazuhiko 京都大学, 大学院工学研究科, 助教 (30712046)
• Project Period (FY): 2010-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥49,530,000 (Direct Cost: ¥38,100,000、Indirect Cost: ¥11,430,000); Fiscal Year 2014: ¥9,620,000 (Direct Cost: ¥7,400,000、Indirect Cost: ¥2,220,000); Fiscal Year 2013: ¥10,140,000 (Direct Cost: ¥7,800,000、Indirect Cost: ¥2,340,000); Fiscal Year 2012: ¥10,660,000 (Direct Cost: ¥8,200,000、Indirect Cost: ¥2,460,000); Fiscal Year 2011: ¥10,530,000 (Direct Cost: ¥8,100,000、Indirect Cost: ¥2,430,000); Fiscal Year 2010: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000)
• Keywords: 協働金属触媒 / 遷移金属 / ルイス酸 / 不活性結合 / 不活性結合活性化 / 炭素ー水素結合活性化 / 炭素ー炭素結合活性化 / 炭素ー酸素結合活性化 / 炭素ー窒素結合活性化 / 炭素-水素結合活性化 / 炭素-炭素結合活性化 / 炭素-炭素結合活性

Outline of Final Research Achievements

We have investigated novel synthetic reactions involving direct activation and functionalization of common chemical bonds of organic molecules by cooperative metal catalysis. We have developed reactions involving C-H and C-C bond activation followed by their functionalization to form new C-C bonds by cooperative Ni/Al catalysis, regioselective borylation of heteroarene C-H bonds by cooperative Ir/Al catalysis, and direct functionalization of C-O and C-N bonds by cooperative Pd/B catalysis.

Research Products

• [Journal Article] Synthesis of Rhazinilam through Intramolecular Arylcyanation of Alkenes Catalyzed Cooperatively by Nickel/Aluminum (2015)
  • Author(s): Yuuya Yamada, Shiro Ebata, Tamejiro Hiyama, Yoshiaki Nakao
  • Journal Title: Tetrahedron Volume: 71 Issue: 26-27 Pages: 4413-4417
  • DOI: 10.1016/j.tet.2015.03.012
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Arylboration of Alkenes by Cooperative Palladium/Copper Catalysis (2014)
  • Author(s): Kazuhiko Semba, Yoshiaki Nakao
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 21 Pages: 7567-7570
  • DOI: 10.1021/ja5029556
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Intramolecular Aminocyanation of Alkenes by Cooperative Palladium/Boron Catalysis (2014)
  • Author(s): Yohsuke Miyazaki, Naoki Ohta, Kazuhiko Semba, Yoshiaki Nakao
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 10 Pages: 3732-3735
  • DOI: 10.1021/ja4122632
  • Peer Reviewed
• [Journal Article] Chemoselective Carbon-Carbon σ-Bond Activation: Nickel/Lewis Acid-Catalyzed Polyfluoro- arylcyanation of Alkynes (2013)
  • Author(s): Yasunori Minami, Hirofumi Yoshiyasu, Yoshiaki Nakao, Tamejiro Hiyama
  • Journal Title: Angewandte Chemie International Edition Volume: 52 Issue: 3 Pages: 883-887
  • DOI: 10.1002/anie.201207880
  • Peer Reviewed
• [Journal Article] Intermolecular Oxycyanation of Alkenes by Cooperative Pd/BPh_3 Catalysis (2012)
  • Author(s): デニスコスター, 小林昌登, ダニエルヴエルツ, 中尾佳亮
  • Journal Title: Journal of the American Chemical Society Volume: 134巻 Issue: 15 Pages: 6544-6547
  • DOI: 10.1021/ja301375c
  • Peer Reviewed
• [Journal Article] Nickel/Lewis Acid-Catalyzed Carbocyanation of Unsaturated Compounds (2012)
  • Author(s): Nakao, Y.
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 85 Issue: 7 Pages: 731-745
  • DOI: 10.1246/bcsj.20120081
  • NAID: 10030785527
  • ISSN: 0009-2673, 1348-0634
  • Peer Reviewed
• [Journal Article] Regioselective Hydrocarbamoylation of 1-Alkenes (2012)
  • Author(s): Yosuke Miyazaki, Yuuya Yamada, Yoshiaki Nakao, Tamejiro Hiyama
  • Journal Title: Chemistry Letters Volume: 41 Issue: 3 Pages: 298-300
  • DOI: 10.1246/cl.2012.298
  • NAID: 10030224504
  • Peer Reviewed
• [Journal Article] Dehydrogenctive [4+2]-Cycloaddition of Formamides with Alkynes through Double C-H Activation (2011)
  • Author(s): Y.Nakao, E.Moroita, H.Idei, T.Hiyama
  • Journal Title: Journal of the American Chemical Society Volume: 131 Pages: 3264-3267
  • Peer Reviewed
• [Journal Article] Selective C-4 Alkylation of Pyridine by Nickel/Lewis Acid Catalysis (2010)
  • Author(s): Y.Nakao, Y.Yamada, N.Kashihara T.Hiyama
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 15996-15997
  • Peer Reviewed
• [Presentation] Cross-coupling Reactions by Cooperative Metal Catalysis (2015)
  • Author(s): Yoshiaki Nakao
  • Organizer: 日本化学会第95春季年会 Lectureship Award MBLA 10周年記念特別講演会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-29
  • Invited
• [Presentation] パラジウム/銅協働触媒によるアルキンのアリールホウ素化反応 (2015)
  • Author(s): 仙波一彦, 吉澤恵, 中尾佳亮
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-28
• [Presentation] C-C Bond Forming Reactions by Cooperative Metal Catalysis (2015)
  • Author(s): Yoshiaki Nakao
  • Organizer: 日本化学会第95春季年会 テトラへドロン受賞シンポジウム
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-27
  • Invited
• [Presentation] ニッケル/アルミニウム協働触媒による安息香酸アミドのパラ位選択的アルキル化反応 (2015)
  • Author(s): 奥村省吾, 齊藤輝彦, 仙波一彦, 中尾佳亮
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-26
• [Presentation] Selective C-4 Borylation of Pyridine by Iridium/Aluminum Cooperative Catalysis (2015)
  • Author(s): Yang Lichen, 齋藤輝彦, 仙波一彦, 中尾佳亮
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-26
• [Presentation] Intramolecular Oxy- and Aminocyanation of Alkenes by Cooperative Palladium/Boron Catalysis (2014)
  • Author(s): Yoshiaki Nakao
  • Organizer: The 9th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-9)/The 5th New Phase International Conference on Cutting-Edge Organic Chemistry in Asia (NICCEOCA-5)
  • Place of Presentation: Petaling Jaya
  • Year and Date: 2014-12-03
• [Presentation] 協働金属触媒による炭素ー炭素結合形成反応 (2014)
  • Author(s): 中尾佳亮
  • Organizer: 第68回有機合成化学協会関東支部シンポジウム（新潟シンポジウム）
  • Place of Presentation: 新潟大学
  • Year and Date: 2014-11-30
  • Invited
• [Presentation] Arene Alkylation by Nickel Catalysis (2014)
  • Author(s): Yoshiaki Nakao
  • Organizer: Progress in Catalytic C-H Activation over the Past Twenty Years (The Murai Symposium)
  • Place of Presentation: Nara
  • Year and Date: 2014-10-30
  • Invited
• [Presentation] Carbocyanation of Unsaturated Bonds through C-CN Activation (2014)
  • Author(s): Yoshiaki Nakao
  • Organizer: Conference on C-C Bond Cleavage
  • Place of Presentation: Kyoto
  • Year and Date: 2014-10-24
  • Invited
• [Presentation] Ni/Al協働触媒によるアニリド類及び安息香酸アミド類のアルキル化反応 (2014)
  • Author(s): 奥村省吾, 小峰卓也, 仙波一彦, 中尾佳亮
  • Organizer: 第4回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2014-10-16
• [Presentation] アルケンの分子内不斉アミノシアノ化反応 (2014)
  • Author(s): 多田直樹, 仙波一彦, 中尾佳亮
  • Organizer: 第4回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2014-10-16
• [Presentation] アルケンの分子内不斉アミノシアノ化反応 (2014)
  • Author(s): 多田直樹, 仙波一彦, 中尾佳亮
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学
  • Year and Date: 2014-09-25
• [Presentation] Ni/Al協働触媒によるアニリド類及び安息香酸アミド類のアルキル化反応 (2014)
  • Author(s): 奥村省吾, 小峰卓也, 仙波一彦, 中尾佳亮
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学
  • Year and Date: 2014-09-25
• [Presentation] パラジウム/銅協働触媒によるアルケンのアリールホウ素化反応 (2014)
  • Author(s): 仙波一彦, 中尾佳亮
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学
  • Year and Date: 2014-09-23
• [Presentation] アルケンの分子内不斉アミノシアノ化反応 (2014)
  • Author(s): 多田直樹, 仙波一彦, 中尾佳亮
  • Organizer: 第47回有機金属若手の会 夏の学校
  • Place of Presentation: 休暇村大久野島
  • Year and Date: 2014-09-02
• [Presentation] 協働金属触媒による炭素ー炭素結合形成反応 (2014)
  • Author(s): 中尾佳亮
  • Organizer: 第47回有機金属若手の会 夏の学校
  • Place of Presentation: 休暇村大久野島
  • Year and Date: 2014-09-02
  • Invited
• [Presentation] 触媒を複合利用して新反応をみつける (2014)
  • Author(s): 中尾佳亮
  • Organizer: 有機合成夏期セミナー「明日の有機合成化学」
  • Place of Presentation: 大阪科学技術センター
  • Year and Date: 2014-08-28
  • Invited
• [Presentation] C-C Bond Forming Reactions by Cooperative Metal Catalysis (2014)
  • Author(s): Yoshiaki Nakao
  • Organizer: ICOMC2014 Post-Symposium in Okayama
  • Place of Presentation: Okayama
  • Year and Date: 2014-07-20
  • Invited
• [Presentation] Arylboration of Alkenes by Cooperative Palladium/Copper Catalysis (2014)
  • Author(s): Kazuhiko Semba, Yoshiaki Nakao
  • Organizer: The 26th International Conference on Organometallic Chemistry
  • Place of Presentation: Sapporo
  • Year and Date: 2014-07-17
• [Presentation] Intramolecular Aminocyanation of Alkenes by Cooperative Palladium/Boron Catalysis (2014)
  • Author(s): Naoki Ohta, Yosuke Miyazaki, Kazuhiko Semba, Yoshiaki Nakao
  • Organizer: The 26th International Conference on Organometallic Chemistry
  • Place of Presentation: Sapporo
  • Year and Date: 2014-07-15
• [Presentation] C-C Bond Forming Reactions by Cooperative Metal Catalysis (2014)
  • Author(s): Yoshiaki Nakao
  • Organizer: The 19th International Symposium on Homogeneous Catalysis (ISHC-19)
  • Place of Presentation: Ottawa
  • Year and Date: 2014-07-09
  • Invited
• [Presentation] 協働金属触媒による炭素ー炭素結合形成反応 (2014)
  • Author(s): 中尾佳亮
  • Organizer: 理研シンポジウム「有機合成化学を起点とするものづくり戦略」
  • Place of Presentation: 理化学研究所
  • Year and Date: 2014-06-09
  • Invited
• [Presentation] C-C Bond Forming Reactions by Cooperative Metal Catalysis (2014)
  • Author(s): Yoshiaki Nakao
  • Organizer: The International Start-up Symposium of Cutting-Edge Organic Chemistry in Asia III
  • Place of Presentation: Hsinchu
  • Year and Date: 2014-04-20
  • Invited
• [Presentation] 協働金属触媒による炭素―炭素結合形成付加反応 (2014)
  • Author(s): 中尾佳亮
  • Organizer: 研究会「金属新機能場の開発を目指して」
  • Place of Presentation: 豊中市
  • Invited
• [Presentation] Intraomolecular Oxy- and Aminocyanation of Alkenes by Cooperative Catalysis (2013)
  • Author(s): Yoshiaki Nakao
  • Organizer: 1st Asian Conference for “MONODUKURI” Strategy by Synthetic Organic Chemistry
  • Place of Presentation: Okinawa
  • Invited
• [Presentation] C–H Functionalization by Cooperative Nickel/Aluminum Catalysis (2013)
  • Author(s): Yoshiaki Nakao
  • Organizer: 3rd International Symposium on Molecular Activation
  • Place of Presentation: Steamboat, USA
  • Invited
• [Presentation] Cyanofunctionalization by Cooperative Catalysis (2012)
  • Author(s): Yoshiaki Nakao
  • Organizer: Cambodian Malaysian Chemical Conference
  • Place of Presentation: Siem Reap, Cambodia
  • Year and Date: 2012-10-19
  • Invited
• [Presentation] Cyanofunctionalization by Cooperative Catalysis (2012)
  • Author(s): Yoshiaki Nakao
  • Organizer: 7th Asian#8211;European Symposium on Metal-Mediated Efficient Organic Synthesis
  • Place of Presentation: ICIQ, Tarragona, Spain
  • Year and Date: 2012-07-23
  • Invited
• [Presentation] C-C Bond Forming Addition Reactions by Cooperative Metal Catalysis (2011)
  • Author(s): Yoshiaki Nakao
  • Organizer: RIKEN International Symposium on Frontiers of Organometallic Chemistry
  • Place of Presentation: RIKEN(埼玉県)(招待講演)
  • Year and Date: 2011-11-04
• [Presentation] 協働金属触媒による炭素-炭素結合形成付加反応 (2010)
  • Author(s): 中尾佳亮
  • Organizer: 20周年記念万有福岡
  • Place of Presentation: 九州大学医学部百年講堂(福岡市)(招待講演)
  • Year and Date: 2010-05-22
• [Presentation] 協働金属触媒による炭素―炭素結合形成付加反応
  • Author(s): 中尾佳亮
  • Organizer: 近畿化学協会 有機金属部会 平成25年度第3回例会
  • Place of Presentation: 札幌市
  • Invited