アート錯体の精密制御によるヘテロ芳香環の開環と原子挿入

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 18H04254
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Kyoto University
• Principal Investigator: 依光 英樹 京都大学, 理学研究科, 教授 (00372566)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: アザボリン / ヘテロ芳香環 / アート錯体 / 炭素－窒素結合切断 / 銅 / シリル化 / ベンゾフラン / 開環 / マンガン

Outline of Annual Research Achievements

我々は、アート錯体を用いてピロール類縁体の開裂と原子挿入を実現する手法を探索した。その結果、アート錯体では反応がうまくいかなかったものの、金属リチウムによる還元的ジリチオ化を利用することでインドールのC-N結合が切断され、対応するジアニオン種が生成することを明らかにした。インドールに対してTHF溶媒中-30℃で5当量のリチウム粉末を作用させることで目的の開環ジリチオ化が進行し、プロトン化の後2-ビニルアニリンが95%の収率で得られることを明らかにした。続いて、開環ジリチオ化中間体に対しホウ素求電子剤を作用させることで、インドールに対するホウ素挿入を試みた。開環ジリチオ化中間体を発生させた後、反応溶液に残存するリチウム粉末をアルゴン雰囲気下においてガラスフィルターにより取り除き、得られた溶液に対し有機ボロン酸ピナコールエステルを加えた。すると期待した通りホウ素が挿入されたベンズアザボリンが得られた。本反応には様々な有機ボロン酸ピナコールエステルを適用することができ、多くの新規ベンズアザボリンの合成に成功した。ホウ素挿入過程は非常に速やかに進行し、トリフルオロメチル基やケトン、エステルなどの官能基を有するホウ素求電子剤からも問題なく目的物が得られた。さらにピリジン環やアルキル基など様々な置換基を有するベンズアザボリンの合成にも成功した。また、orthoブロモフェニル基を持つアザボリンに対しパラジウム触媒を用いた分子内C-Hアリール化を施すことで、分子内にBN構造を有する多環式芳香族化合物の合成にも成功した。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] カタロニア触媒化学研究所(スペイン)
• [Int'l Joint Research] デリー大学(インド)
• [Int'l Joint Research] Columbia University(米国)
• [Journal Article] Ni-Catalyzed Carboxylation of C(sp2)?S Bonds with CO2: Evidence for the Multifaceted Role of Zn (2020)
  • Author(s): Yanagi Tomoyuki、Somerville Rosie J.、Nogi Keisuke、Martin Ruben、Yorimitsu Hideki
  • Journal Title: ACS Catalysis Volume: 10 Issue: 3 Pages: 2117-2123
  • DOI: 10.1021/acscatal.9b05141
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Tf2O-mediated Reaction of Alkenyl Sulfoxides with Unprotected Anilines in Flow Microreactors (2020)
  • Author(s): Baralle Alexandre、Inukai Tomoaki、Yanagi Tomoyuki、Nogi Keisuke、Osuka Atsuhiro、Nagaki Aiichiro、Yoshida Jun-ichi、Yorimitsu Hideki
  • Journal Title: Chemistry Letters Volume: 49 Issue: 2 Pages: 160-163
  • DOI: 10.1246/cl.190831
  • NAID: 130007795212
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Reductive Difunctionalization of Aryl Alkenes with Sodium Metal and Reduction-Resistant Alkoxy-Substituted Electrophiles (2020)
  • Author(s): Fukazawa Mizuki、Takahashi Fumiya、Nogi Keisuke、Sasamori Takahiro、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 22 Issue: 6 Pages: 2303-2307
  • DOI: 10.1021/acs.orglett.0c00490
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Amination of Aryl Sulfides and Sulfoxides with Azaarylamines of Poor Nucleophilicity (2019)
  • Author(s): Pratap Ramendra、Yorimitsu Hideki
  • Journal Title: Synthesis Volume: 51 Issue: 13 Pages: 2705-2712
  • DOI: 10.1055/s-0037-1611732
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Palladium-Catalyzed Alkoxycarbonylation of Arylsulfoniums (2019)
  • Author(s): Minami Hiroko、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 21 Issue: 8 Pages: 2518-2522
  • DOI: 10.1021/acs.orglett.9b00067
  • NAID: 120006621582
  • Peer Reviewed / Open Access
• [Journal Article] Aromatic Metamorphosis of Indoles into 1,2-Benzazaborins (2019)
  • Author(s): Tsuchiya Shun、Saito Hayate、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 21 Issue: 10 Pages: 3855-3860
  • DOI: 10.1021/acs.orglett.9b01353
  • Peer Reviewed
• [Journal Article] Diborative Reduction of Alkynes to 1,2-Diboryl-1,2-Dimetalloalkanes: Its Application for the Synthesis of Diverse 1,2-Bis(boronate)s (2019)
  • Author(s): Takahashi Fumiya、Nogi Keisuke、Sasamori Takahiro、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 21 Issue: 12 Pages: 4739-4744
  • DOI: 10.1021/acs.orglett.9b01622
  • Peer Reviewed
• [Journal Article] Copper-Catalyzed Twofold Silylmetalation of Alkynes (2019)
  • Author(s): Yamagishi Hiroki、Shimokawa Jun、Yorimitsu Hideki
  • Journal Title: Synlett Volume: 30 Issue: 13 Pages: 1551-1554
  • DOI: 10.1055/s-0037-1611869
  • NAID: 120006715508
  • Peer Reviewed
• [Journal Article] Synthesis of N-Alkyl and N-H Carbazoles via SNAr‐based Aminations of Dibenzothiophene dioxides (2019)
  • Author(s): Kaga Atsushi、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Chemistry - A European Journal Volume: 25 Issue: 65 Pages: 14780-14784
  • DOI: 10.1002/chem.201903916
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Arylthiolation of Alkynes Enabled by Surmounting Competitive Dimerization of Alkynes (2019)
  • Author(s): Uno Daisuke、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 21 Issue: 20 Pages: 8295-8299
  • DOI: 10.1021/acs.orglett.9b03056
  • Peer Reviewed
• [Journal Article] Cross-Coupling of Aryl Trifluoromethyl Sulfones with Arylboronates by Cooperative Palladium/Rhodium Catalysis (2019)
  • Author(s): Fukuda Jun-ichi、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 21 Issue: 22 Pages: 8987-8991
  • DOI: 10.1021/acs.orglett.9b03393
  • NAID: 120006800717
  • Peer Reviewed
• [Journal Article] Construction of Biaryls from Aryl Sulfoxides and Anilines by Means of a Sigmatropic Rearrangement (2019)
  • Author(s): Yanagi Tomoyuki、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Chemistry A European Journal Volume: 26 Issue: 4 Pages: 783-787
  • DOI: 10.1002/chem.201903570
  • NAID: 120006800745
  • Peer Reviewed
• [Journal Article] Sulfoxide-Directed Iterative Assembly into Oligoarenes (2019)
  • Author(s): Yanagi Tomoyuki、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Synlett Volume: 印刷中 Issue: 02 Pages: 153-157
  • DOI: 10.1055/s-0037-1611767
  • Peer Reviewed
• [Journal Article] Annulative Synthesis of Benzofurans from General Alkenyl Sulfoxides and Phenols via Pummerer/Sigmatropic Cascade (2019)
  • Author(s): Hori Mitsuki、Yanagi Tomoyuki、Murakami Kei、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 92 Issue: 2 Pages: 302-311
  • DOI: 10.1246/bcsj.20180321
  • NAID: 130007593735
  • Peer Reviewed
• [Journal Article] Photoredox-Catalyzed Alkenylation of Benzylsulfonium Salts (2019)
  • Author(s): Otsuka Shinya、Nogi Keisuke、Rovis Tomislav、Yorimitsu Hideki
  • Journal Title: Chemistry - An Asian Journal Volume: 14 Issue: 4 Pages: 532-536
  • DOI: 10.1002/asia.201801732
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Palladium-Catalyzed Homo-Coupling of Heteroarylsulfoniums via Borylation/Suzuki-Miyaura Coupling Sequence (2018)
  • Author(s): Minami Hiroko、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: HETEROCYCLES Volume: 97 Issue: 2 Pages: 998-998
  • DOI: 10.3987/com-18-s(t)78
  • Peer Reviewed
• [Journal Article] Palladium‐Catalyzed Insertion of Isocyanides into the C‐S Bonds of Heteroaryl Sulfides (2018)
  • Author(s): Otsuka Shinya、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Angewandte Chemie - International Edition Volume: 印刷中 Issue: 22 Pages: 6653-6657
  • DOI: 10.1002/anie.201802369
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Mizoroki-Heck-Type Alkenylation of Monoaryldialkylsulfoniums (2018)
  • Author(s): Uno Daisuke、Minami Hiroko、Otsuka Shinya、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Chemistry - An Asian Journal Volume: 13 Issue: 17 Pages: 2397-2400
  • DOI: 10.1002/asia.201800489
  • Peer Reviewed
• [Journal Article] “Macroscopically Anisotropic Structures Produced by Lightinduced Solvothermal Assembly of Porphyrin Dimers” (2018)
  • Author(s): Y. Yamamoto, Y. Nishimura, S. Tokonami, N. Fukui, T. Tanaka, A. Osuka, H. Yorimitsu, and T. Iida
  • Journal Title: Sci. Rep. Volume: 8 Issue: 1 Pages: 11108-11108
  • DOI: 10.1038/s41598-018-28311-2
  • NAID: 120006539601
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Copper-Catalyzed Ring-Opening Silylation of Benzofurans with Disilane (2018)
  • Author(s): Saito Hayate、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 34 Pages: 11030-11034
  • DOI: 10.1002/anie.201806237
  • Peer Reviewed
• [Journal Article] Synthesis of 4-aryl- and 4-acyl-1,3-dithiole-2-thiones via deprotonative zincation of 1,3-dithiole-2-thione (2018)
  • Author(s): Otsuka Shinya、Yorimitsu Hideki
  • Journal Title: Heteroatom Chemistry Volume: 29 Issue: 3
  • DOI: 10.1002/hc.21432
  • Peer Reviewed
• [Journal Article] Cobalt-Catalyzed Reduction of Aryl Sulfones to Arenes by Means of Alkylmagnesium Reagents (2018)
  • Author(s): Fukuda Jun-ichi、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Asian Journal of Organic Chemistry Volume: 7 Issue: 10 Pages: 2049-2052
  • DOI: 10.1002/ajoc.201800473
  • Peer Reviewed
• [Journal Article] Sigmatropic Dearomatization/Defluorination Strategy for C-F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols (2018)
  • Author(s): Okamoto Koichi、Hori Mitsuki、Yanagi Tomoyuki、Murakami Kei、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 43 Pages: 14230-14234
  • DOI: 10.1002/anie.201809035
  • Peer Reviewed
• [Journal Article] Intramolecular Desulfitative Coupling: Nickel-Catalyzed Transformation of Diaryl Sulfones into Biaryls via Extrusion of SO2 (2018)
  • Author(s): Takahashi Fumiya、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Organic Letters Volume: 20 Issue: 20 Pages: 6601-6605
  • DOI: 10.1021/acs.orglett.8b02972
  • Peer Reviewed
• [Journal Article] Recent development of ortho -C?H functionalization of aryl sulfoxides through [3,3] sigmatropic rearrangement (2018)
  • Author(s): Yanagi Tomoyuki、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Tetrahedron Letters Volume: 59 Issue: 31 Pages: 2951-2959
  • DOI: 10.1016/j.tetlet.2018.06.055
  • Peer Reviewed
• [Journal Article] C-S Bond Activation (2018)
  • Author(s): Otsuka Shinya、Nogi Keisuke、Yorimitsu Hideki
  • Journal Title: Topics in Current Chemistry Volume: 376 Issue: 2 Pages: 13-13
  • DOI: 10.1007/s41061-018-0190-7
  • NAID: 120006621579
  • Peer Reviewed
• [Presentation] Seven-membered Dialkoxysilyl Group Activatable under Specific Conditions (2020)
  • Author(s): Hayate Saito, Jun Shimokawa, Hideki Yorimitsu
  • Organizer: Nanyang Research Conference on Synthetic Chemistry and Catalysis
  • Int'l Joint Research
• [Presentation] 7員環構造を有するジアルコキシシリル基の開発と利用 (2020)
  • Author(s): 齊藤颯・下川淳・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] 金属リチウムを用いた還元的ジリチオ化に基づくチオフェン環の芳香環メタモルフォシス (2020)
  • Author(s): 加賀敦志・野木馨介・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] 新規ケイ素官能基供与体ジシラノラートの開発と利用 (2020)
  • Author(s): 山岸拓幹・下川淳・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] ニッケル触媒によるアリールスルホニウム塩の還元的亜鉛化 (2020)
  • Author(s): 山田航大・柳智征・野木馨介・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] 金属ナトリウムを用いたN-アリールピロールの還元的脱アリール化 (2020)
  • Author(s): 西淳一郎・加賀敦志・野木馨介・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] プロパルギルアミンに対する位置選択的なシリルリチウムの付加反応 (2020)
  • Author(s): 佐藤友彦・Somnath Karad・下川淳・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] 銅触媒を用いたトリアルコキシアリールシランの求電子的アミノ化反応 (2020)
  • Author(s): 一入賢之朗・齊藤颯・下川淳・依光英樹
  • Organizer: 日本化学会第100春季年会
• [Presentation] Aromatic Metamorphosis: Breaking Aromaticity to Construct New Cyclic Systems (2019)
  • Author(s): Hideki Yorimitsu
  • Organizer: The 1st KU-UNIST Joint Symposium on Chemistry and Materials Science
  • Int'l Joint Research / Invited
• [Presentation] Aromatic Metamorphosis of Benzofurans (2019)
  • Author(s): Hideki Yorimitsu
  • Organizer: International Symposium of Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research / Invited
• [Presentation] Aromatic Metamorphosis for the Synthesis of Azaarenes (2019)
  • Author(s): Hideki Yorimitsu
  • Organizer: The 2nd Sino-Japanese Symposium on Catalysis for Precision Synthesis
  • Int'l Joint Research / Invited
• [Presentation] Copper-Catalyzed Ring-Opening Silylation of Benzofurans with Disilane (2019)
  • Author(s): Hayate Saito, Keisuke Nogi, Hideki Yorimitsu
  • Organizer: The 20th IUPAC Conference on Organometallic Chemistry Directed Towards Organic Synthesis
  • Int'l Joint Research
• [Presentation] Nickel-Catalyzed Carboxylation of Arylsulfoniums (2019)
  • Author(s): Tomoyuki Yanagi, Keisuke Nogi, Ruben Martin, and Hideki Yorimitsu
  • Organizer: The 20th IUPAC Conference on Organometallic Chemistry Directed Towards Organic Synthesis
  • Int'l Joint Research
• [Presentation] Copper-catalyzed Twofold Silylmetalation of Alkynes (2019)
  • Author(s): Hiroki Yamagishi, Jun Shimiokawa, Hideki Yorimitsu
  • Organizer: The 20th IUPAC Conference on Organometallic Chemistry Directed Towards Organic Synthesis
  • Int'l Joint Research
• [Presentation] Methylsulfanyl group: multipotent directing group for palladium-catalyzed C_H iodination of arenes (2019)
  • Author(s): Keisuke Nogi, Keita Yamamoto, Ling-Jun Liu, Hideki Yorimitsu
  • Organizer: The 47th Naito Conference on C_C Bond Activation and Transformation
  • Int'l Joint Research
• [Presentation] アルカリ金属強塩基を用いたジベンゾチオフェンからN－アルキルカルバゾールへの芳香環変換反応 (2019)
  • Author(s): 加賀敦志・野木馨介・依光英樹
  • Organizer: 第36回有機合成化学セミナー
• [Presentation] 銅触媒を用いたアルキンの二重シリルメタル化 (2019)
  • Author(s): 山岸拓幹・下川淳・依光英樹
  • Organizer: 第36回有機合成化学セミナー
• [Presentation] パラジウム触媒を用いたアリールスルホキシドのC_Hアルコキシ化 (2019)
  • Author(s): 佐藤友彦・野木馨介・依光英樹
  • Organizer: 第36回有機合成化学セミナー
• [Presentation] パラジウム触媒を用いたアリールスルホキシドのC_Hアルコキシ化 (2019)
  • Author(s): 佐藤友彦・野木馨介・依光英樹
  • Organizer: 第66回有機金属化学討論会
• [Presentation] Four-component Coupling Strategy for 2,3,4-trisubstituted 3,4-Dihydroquinoline (2019)
  • Author(s): Hiroki Yamagishi, Shun Tsuchiya, Hayate Saito, Keisuke Nogi, Jun Shimiokawa, Hideki Yorimitsu
  • Organizer: 27th International Society of Heterocyclic Chemistry Congress
  • Int'l Joint Research
• [Presentation] 安定性と反応性の両立を指向したアルコキシシリル基の開発 (2019)
  • Author(s): 齊藤颯・下川淳・依光英樹
  • Organizer: 第46回有機典型元素化学討論会
• [Presentation] Copper-Catalyzed Ring-Opening Silylation of Benzofurans with Disilane (2019)
  • Author(s): Hayate Saito, Keisuke Nogi, Hideki Yorimitsu
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] 高エネルギースルホニウムカチオンが拓く高難度分子変換 (2019)
  • Author(s): 依光英樹
  • Organizer: 日本化学会第99春季年会「特別企画」未来機能を生み出すp-ブロック統合化学
  • Invited
• [Presentation] Aromatic Metamorphosis: Conversions of Heteroaromatic Skeletons into Different Rings (2018)
  • Author(s): Hideki Yorimitsu
  • Organizer: The 1st Sino-Japanese Symposium on Catalysis for Precision Synthesis
  • Int'l Joint Research / Invited
• [Presentation] 芳香環の破壊をもたらす遷移金属触媒反応 (2018)
  • Author(s): 依光英樹
  • Organizer: 第7回錯体化学若手の会 九州・沖縄支部勉強会
  • Invited
• [Remarks] 研究室HP
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/
• [Remarks] 「驚きの有機化学反応を創り育てる」 京都大学理学研究科・理学部研究紹介インタビュー
  • URL: http://www.sci.kyoto-u.ac.jp/ja/research/activities-ch/1910-hidekiyorimitsu.html
• [Remarks] 化学専攻 依光英樹教授が日本学術振興会賞を受賞
  • URL: http://www.sci.kyoto-u.ac.jp/ja/news/detail_1557.html
• [Remarks] 化学専攻 依光英樹教授が日本学士院学術奨励賞を受賞
  • URL: http://www.sci.kyoto-u.ac.jp/ja/news/detail_1575.html
• [Remarks] 依光英樹 理学研究科教授が第16回（令和元年度）日本学士院学術奨励賞を受賞
  • URL: http://www.kyoto-u.ac.jp/ja/about/events_news/office/soumu/koho/news/2019/200114_1.html