カルボキシル基を配向基とする炭素―水素および炭素―炭素結合の直截的変換法の開発

• Project Area: Molecule Activation Directed toward Straightforward Synthesis
• Project/Area Number: 25105733
• 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: Osaka University
• Principal Investigator: 佐藤 哲也 大阪大学, 工学(系)研究科(研究院), 准教授 (40273586)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: 炭素-水素結合活性化 / ロジウム触媒 / 酸化的カップリング / カルボン酸 / 炭素ー水素結合活性化

Outline of Annual Research Achievements

遷移金属触媒を用いる炭素－水素および炭素－炭素結合切断を経る直截的炭素－炭素結合形成反応は、ステップおよびアトムエコノミーの観点から有用な有機合成手法として近年注目されている。そのような反応は、炭素－炭素結合形成法として従来用いられてきたクロスカップリング反応に比べ、反応工程の単純化および副生物の大幅な低減をもたらす。ユビキタスな炭素－水素あるいは炭素－炭素結合を、位置選択的に切断するための最も有力な手法として、配向基を利用したオルトメタル化を経る反応が挙げられる。我々はこれまでに、カルボキシル基を配向基とし、その近傍でのアリール化、アルケニル化、あるいは環化を効率よく行うことに成功している。本研究では、これまでに開発したIII価ロジウム触媒系を駆使してカルボン酸類の誘導体化法について検討を行う中で、2,2-ジフェニルアルカン酸類の脱炭酸を伴う分子内脱水素アリール―アリールカップリングおよび関連反応について検討を行ったので、結果を報告する。
まず、2,2-ジフェニルアルカン酸類を、ロジウム―銅触媒およびピバル酸存在下、空気雰囲気で反応させると、脱水素環化が効率よく進行し、フルオレン誘導体を良好な種率で与えることを見出した。従来の量論量銅塩を酸化剤として用いる反応に比べ、系がクリーンである。さらに類似のロジウム触媒系を用いると、ジチアンやホスフィンスルフィド等の、これまで配向基として利用されていない含硫黄官能基の近傍でも炭素―水素結合が切断され、直截的脱水素カップリングが行えることも明らかになった。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Rhodium(III)-Catalyzed Oxidative Alkenylation of 1,3-Dithiane-Protected Arenecarbaldehydes via Regioselective C-H Bond Cleavage (2015)
  • Author(s): Y. Unoh, K. Hirano, T. Satoh, M. Miura
  • Journal Title: Organic Letters Volume: 17 Issue: 3 Pages: 704-707
  • DOI: 10.1021/ol503722r
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Rhodium-Catalyzed Dehydrogenative Coupling of Phenylheteroarenes with Alkynes or Alkenes (2015)
  • Author(s): 飯塚 智紀
  • Journal Title: J. Org. Chem. Volume: 80 Issue: 5 Pages: 2804-2814
  • DOI: 10.1021/acs.joc.5b00155
  • Peer Reviewed
• [Journal Article] Direct Synthesis of N-H Carbazoles via Iridium(III)-Catalyzed Intramolecular C-H Amination (2015)
  • Author(s): 鈴木 智晴
  • Journal Title: Org. Lett. Volume: 17 Issue: 6 Pages: 1597-1600
  • DOI: 10.1021/acs.orglett.5b00502
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzed direct ortho-alkenylation of phenyl sulfones with alkynes utilizing sulfonyl function as modifiable directing group (2015)
  • Author(s): 信重 和紀
  • Journal Title: Tetrahedron Volume: 印刷中 Issue: 37 Pages: 6506-6512
  • DOI: 10.1016/j.tet.2015.03.046
  • Peer Reviewed / Open Access
• [Journal Article] Copper-Catalyzed α-Methylenation of Benzylpyridines Using Dimethylacetamide as One-Carbon Source (2014)
  • Author(s): 伊藤 将城
  • Journal Title: Org. Lett. Volume: 16 Issue: 7 Pages: 2050-2053
  • DOI: 10.1021/ol500655k
  • Peer Reviewed
• [Journal Article] Ruthenium- and Rhodium-Catalyzed Dehydrogenative ortho-Alkenylation of Benzyl Amines via Free Amino Group Directed C-H Bond Cleavage (2014)
  • Author(s): 鈴木 智晴
  • Journal Title: Adv. Synth. Catal. Volume: 356 Issue: 7 Pages: 1521-1526
  • DOI: 10.1002/adsc.201400088
  • Peer Reviewed
• [Journal Article] Oxidative Annulation of Tertiary Benzyl Alcohols with Internal Alkynes Using an (Electron-Deficient η5-Cyclopentadienyl)Rhodium(III) Catalyst Under Ambient Conditions (2014)
  • Author(s): M. Fukui, Y. Hoshino, T. Satoh, M. Miura, K. Tanaka
  • Journal Title: Adv. Synth. Catal. Volume: 356 Issue: 7 Pages: 1638-1644
  • DOI: 10.1002/adsc.201400084
  • Peer Reviewed
• [Journal Article] Rhodium(III)-Catalyzed Regioselective C-H Alkenylation of Phenylphosphine Sulfides (2014)
  • Author(s): Y. Yokoyama, Y, Unoh, K. Hirano, T. Satoh, M. Miura
  • Journal Title: The Journal of Organic Chemistry Volume: 79 Issue: 16 Pages: 7649-7655
  • DOI: 10.1021/jo501542b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Unexpected Cyclization of Tritylamines Promoted by Copper Salt through C-H and C-N Bond Cleavages to Produce Acridine Derivatives (2014)
  • Author(s): 森岡 亮介
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 40 Pages: 12720-12724
  • DOI: 10.1002/chem.201404656
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Intramolecular Dehydrogenative Aryl-Aryl Coupling Using Air as Terminal Oxidant (2014)
  • Author(s): H. Baars, Y. Unoh, T, Okada, K. Hirano, T. Satoh, K, Tanaka, C, Bolm, M. Miura
  • Journal Title: Chemistry Letters Volume: 43 Issue: 11 Pages: 1782-1784
  • DOI: 10.1246/cl.140690
  • NAID: 130004677604
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Palladium-Catalyzed Decarboxylative Arylation of Benzoylacrylic Acids toward the Synthesis of Chalcones (2013)
  • Author(s): Yuto Unoh, Koji Hirano, Tetsuya Satoh, Masahiro Miura
  • Journal Title: The Journal of Organic Chemistry Volume: 78 Issue: 10 Pages: 5096-5102
  • DOI: 10.1021/jo400716e
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed Direct Alkylation of Heterocycles with α-Bromo Carbonyl Compounds: C3-Selective Functionalization of 2-Pyridones (2013)
  • Author(s): Nakatani Akihiro, Koji Hirano, Tetsuya Satoh, Masahiro Miura
  • Journal Title: Chemistry - A European Journal Volume: 19 Issue: 24 Pages: 7691-7695
  • DOI: 10.1002/chem.201301350
  • Peer Reviewed
• [Journal Article] Rhodium(III)-catalyzed Oxidative Coupling through C–H Bond Cleavage Directed by Phosphinoxy Groups (2013)
  • Author(s): Yuto Unoh, Yuto Hashimoto, Daisuke Takeda, Koji Hirano, Tetsuya Satoh and Masahiro Miura
  • Journal Title: Organic Letters Volume: 15 Issue: 13 Pages: 3258-3261
  • DOI: 10.1021/ol4012794
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed C3-Selective Alkenylation of Substituted Thiophene-2-Carboxylic Acids and Related Compounds (2013)
  • Author(s): Tomonori Iitsuka, Petra Schaal, Koji Hirano, Tetsuya Satoh, Carsten Bolm and Masahiro Miura
  • Journal Title: The Journal of Organic Chemistry Volume: 78 Issue: 14 Pages: 7216-7222
  • DOI: 10.1021/jo4011969
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Regioselective C-H Alkenylation Directed by a Free Amino Group (2013)
  • Author(s): Chiharu Suzuki, Koji Hirano, Tetsuya Satoh, Masahiro Miura
  • Journal Title: Organic Letters Volume: 15 Issue: 15 Pages: 3990-3993
  • DOI: 10.1021/ol401779h
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed ortho-Alkenylation of Phenylphosphine Oxides through Regio- and Stereoselective Alkyne Insertion into C-H Bond (2013)
  • Author(s): Masaki Itoh, Yuto Hashimoto, Koji Hirano, Tetsuya Satoh and Masahiro Miura
  • Journal Title: The Journal of Organic Chemistry Volume: 78 Issue: 16 Pages: 8098-8104
  • DOI: 10.1021/jo401393b
  • Peer Reviewed
• [Journal Article] An Approach to Benzophosphole Oxides through Silver- or Manganese-Mediated Dehydrogenative Annulation Involving C-C and C-P Bond Formation (2013)
  • Author(s): Yuto Unoh, Koji Hirano, Tetsuya Satoh, Masahiro Miura
  • Journal Title: Angewandte Chemie International Edition Volume: 52 Issue: 49 Pages: 12975-12979
  • DOI: 10.1002/anie.201307211
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Decarboxylative and Dehydrogenative Coupling of Maleic Acids with Alkynes and Alkenes (2013)
  • Author(s): Masaki Itoh, Masaki Shimizu, Koji Hirano, Tetsuya Satoh and Masahiro Miura
  • Journal Title: The Journal of Organic Chemistry Volume: 78 Issue: 22 Pages: 11427-11432
  • DOI: 10.1021/jo401992d
  • Peer Reviewed
• [Presentation] Rhodium- and Ruthenium-Catalyzed Regioselective C-H Functionalization (2014)
  • Author(s): 佐藤 哲也
  • Organizer: The 41st International Conference on Coordination Chemistry
  • Place of Presentation: Suntec Singapore Convention & Exhibition Centre (Singapore)
  • Year and Date: 2014-07-21
  • Invited
• [Presentation] C-H 官能基化 (2014)
  • Author(s): 佐藤 哲也
  • Organizer: 第41 回有機金属化学セミナー
  • Place of Presentation: キャンパスプラザ京都（京都府京都市）
  • Year and Date: 2014-06-06
  • Invited
• [Presentation] カルボン酸類および関連化合物の触媒的直截変換反応 (2014)
  • Author(s): 佐藤 哲也
  • Organizer: 分子活性化第６回公開シンポジウム
  • Place of Presentation: 東京工業大学
  • Invited
• [Presentation] 配向基を利用した芳香環への直接置換基導入法の開発 (2014)
  • Author(s): 佐藤 哲也
  • Organizer: 研究会 金属新機能場の開発を目指して
  • Place of Presentation: 大阪大学
  • Invited
• [Presentation] C-H 官能基化 (2013)
  • Author(s): 佐藤 哲也
  • Organizer: 第40 回有機金属化学セミナー
  • Place of Presentation: キャンパスプラザ京都
  • Invited
• [Presentation] Transition-Metal-Catalyzed Dehydrogenative Coupling through Carboxyl Group-Directed C-H Bond Cleavage (2013)
  • Author(s): 佐藤 哲也
  • Organizer: The 3rd International Symposium on Molecular Activation
  • Place of Presentation: Sheraton Steamboat Resort
  • Invited
• [Presentation] Chelation-Assisted Direct C-H Functionalization under Transition-Metal Catalysis under Transition-Metal Catalysis (2013)
  • Author(s): 佐藤 哲也
  • Organizer: The 15th Asian Chemical Congress
  • Place of Presentation: Resorts World Sentosa Convention Centre
  • Invited
• [Book] Science of Synthesis, (Vol. Catalytic Transformations via C―H Activation) (2015)
  • Author(s): 佐藤 哲也
  • Publisher: Georg Thieme
• [Book] Metal-Catalyzed Cross-Coupling Reactions and More (2014)
  • Author(s): 佐藤 哲也
  • Total Pages: 37
  • Publisher: Wiley-VCH
• [Book] Science of Synthesis, (Vol. Catalytic Transformations via C-H Activation) (2014)
  • Author(s): 佐藤 哲也
  • Publisher: Georg Thieme
• [Book] Transition-Metal-Mediated Aromatic Ring Construction (2013)
  • Author(s): 佐藤 哲也
  • Total Pages: 35
  • Publisher: John Wiley and Sons