Synthesis of Sulfur-Containing Fused Heteroaromatic Compounds via Oxidative Coupling

• Project/Area Number: 22550101
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: SATOH Tetsuya 大阪大学, 大学院・工学研究科, 准教授 (40273586)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2012: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2011: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2010: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 縮合へテロ環 / π共役分子 / 酸化的カップリング / 炭素-水素結合活性化 / ルテニウム触媒 / ロジウム触媒 / パラジウム触媒 / 炭素―水素結合切断 / 縮合環形成 / パイ共役分子合成 / 炭素-水素結合切断 / アルケニル化 / π共役分子合成

Research Abstract

The oxidative coupling reactions of various aromatic substrates with alkynes and alkenes under transition-metal catalysis such as rhodium, palladium, and ruthenium were investigated. As a result, I succeeded in finding a number of new coupling reactions involving C-H bond cleavage. Furthermore, it was successfully shown that a wide range of sulfu- or other heteroatom-containing fused heteroaromatic compounds can be efficiently prepared by using these new reactions.

Research Products

• [Journal Article] Rhodium- and Iridium-Catalyzed Dehydrogenative Cyclization through Double C-H Bond Cleavages To Produce Fluorene Derivatives (2013)
  • Author(s): Masaki Itoh
  • Journal Title: Journal of Organic Chemistry Volume: 78 Issue: 4 Pages: 1365-1370
  • DOI: 10.1021/jo4000465
  • Peer Reviewed
• [Journal Article] Synthesis of highly substituted isocoumarins by rhodium-catalyzed annulation of readily available benzoic acids (2013)
  • Author(s): 宇納 佑斗
  • Journal Title: Tetrahedron Volume: 69 Issue: 22 Pages: 4454-4458
  • DOI: 10.1016/j.tet.2012.11.092
  • Peer Reviewed
• [Journal Article] Synthesis of N-Vinylcarbazoles via Dehydrogenative Coupling of N-H Carbazoles with Alkenes under Palladium Catalysis (2013)
  • Author(s): 武田 大介
  • Journal Title: Org. Lett. Volume: 15 Issue: 6 Pages: 1242-1245
  • DOI: 10.1021/ol4001697
  • Peer Reviewed
• [Journal Article] Regioselective C-H Bond Cleavage/Alkyne Insertion under Ruthenium Catalysis (2013)
  • Author(s): 橋本 雄人
  • Journal Title: J. Org. Chem. Volume: 78 Issue: 2 Pages: 638-646
  • DOI: 10.1021/jo3025237
  • Peer Reviewed
• [Journal Article] Synthesis of Fluorene Derivatives through Rhodium-Catalyzed Dehydrogenative Cyclization (2012)
  • Author(s): 佐藤哲也
  • Journal Title: Angew. Chem., Int. Ed Volume: 51巻 Pages: 5359-536
  • Peer Reviewed
• [Journal Article] Synthesis of Phenanthridines and Related Compounds by Palladium-Catalyzed Direct Coupling via C-H and N-H Bond Cleavages (2012)
  • Author(s): 武田 大介
  • Journal Title: Heterocycles Volume: 86 Issue: 1 Pages: 487-496
  • DOI: 10.3987/com-12-s(n)45
  • Peer Reviewed
• [Journal Article] Ruthenium(II)-Catalyzed Regio- and Stereoselective Hydroarylation of Alkynes via Directed C-H Functionalization (2012)
  • Author(s): Hashimoto, Yuto
  • Journal Title: Organic Letters Volume: 14 Issue: 8 Pages: 2058-2061
  • DOI: 10.1021/ol300579m
  • Peer Reviewed
• [Journal Article] Ru/Ag-Catalyzed Oxidative Alkenylation of Benzamides and Phenylazoles through Regioselective C-H Bond Cleavage (2012)
  • Author(s): 橋本 雄人
  • Journal Title: Chem. Lett. Volume: 41 Issue: 2 Pages: 151-153
  • DOI: 10.1246/cl.2012.151
  • NAID: 10030223153
  • Peer Reviewed
• [Journal Article] Effect of the Substitution Pattern of Alkyl Side Chain in a Benzodithiophene Core π-System on Intra and Inter-Molecular Charge Carrier Mobility (2011)
  • Author(s): 佐藤哲也
  • Journal Title: J. Phys. Chem. B Volume: 115巻 Issue: 26 Pages: 8446-8452
  • DOI: 10.1021/jp2036668
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Regioselective Olefination Directed by a Carboxylic Group (2011)
  • Author(s): 佐藤哲也
  • Journal Title: J. Org. Chem Volume: 76巻 Issue: 9 Pages: 3024-3033
  • DOI: 10.1021/jo200509m
  • Peer Reviewed
• [Journal Article] Synthesis of Highly Substituted Acenes through Rhodium-Catalyzed Oxidative Coupling of Arylboron Reagents with Alkynes (2011)
  • Author(s): Fukutani, Tatsuya
  • Journal Title: The Journal of Organic Chemistry Volume: 76 Issue: 8 Pages: 2867-2874
  • DOI: 10.1021/jo200339w
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Oxidative Vinylation of Heteroarene Carboxylic Acids with Alkenes via Regioselective C-H Bond Cleagave (2011)
  • Author(s): 佐藤哲也
  • Journal Title: Org. Lett Volume: 13巻 Issue: 4 Pages: 706-708
  • DOI: 10.1021/ol102942w
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Oxidative 1:1, 1:2, and 1:4 Coupling Reactions of Phenylazoles with Internal Alkynes through the Regioselective Cleavages of Multiple C-H Bonds (2011)
  • Author(s): 佐藤哲也
  • Journal Title: J. Org. Chem Volume: 76巻 Issue: 1 Pages: 13-24
  • DOI: 10.1021/jo1021184
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Oxidative Alkenylation of Arenes via Regio-selective C-H Bond Cleavage Directed by a Nitrogen-Containing Group (2011)
  • Author(s): 橋本 雄人
  • Journal Title: Chem. Lett. Volume: 40 Issue: 10 Pages: 1165-1166
  • DOI: 10.1246/cl.2011.1165
  • NAID: 10029683598
  • Peer Reviewed
• [Journal Article] Synthesis of Isochromene and Related Derivatives by Rhodium-Catalyzed Oxidative Coupling of Benzyl and Allyl Alcohols with Alkynes (2011)
  • Author(s): Morimoto, Keisuke
  • Journal Title: The Journal of Organic Chemistry Volume: 76 Issue: 22 Pages: 9548-9551
  • DOI: 10.1021/jo201923d
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Direct Monoarylation of Thiophene-, Benzothiophene-, and Indoleacetic Acids through Regioselective C-H bond Cleavage (2011)
  • Author(s): 武田 大介
  • Journal Title: Chem. Lett. Volume: 40 Issue: 9 Pages: 1015-1017
  • DOI: 10.1246/cl.2011.1015
  • NAID: 10029522707
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Oxidative Vinylation of Heteroarene Carboxylic Acids with Alkenes via Regioselective C-H Bond Cleagave (2011)
  • Author(s): 上山卓巳
  • Journal Title: Org.Lett. Volume: 13 Pages: 706-708
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Oxidative 1:1, 1:2, and 1:4 Coupling Reactions of Phenylazoles with Internal Alkynes through the Regioselective Cleavages of Multiple C-H Bonds (2011)
  • Author(s): 梅田伸好
  • Journal Title: J.Org.Chem. Volume: 76 Pages: 13-24
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Regioselective Olefination Directed by a Carboxylic Group (2011)
  • Author(s): 望田諭嗣
  • Journal Title: J.Org.Chem. Volume: 76 Pages: 3024-3033
  • Peer Reviewed
• [Journal Article] Synthesis of Highly Substituted Acenes through Rhodium-Catalyzed Oxidative Coupling of Arylboron Reagents with Alkynes (2011)
  • Author(s): 福谷達矢
  • Journal Title: J.Org.Chem. Volume: 76 Pages: 2867-2874
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Oxidative Coupling of Benzylamines with Alkynes through Dehydrogenation and Dehydrogenative Cyclization (2011)
  • Author(s): 森本圭亮
  • Journal Title: Chem.Lett. Volume: 40 Pages: 600-602
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Oxidative Coupling/Cyclization of Benzamides with Alkynes via C-H Bond Cleavage (2010)
  • Author(s): 望田諭嗣
  • Journal Title: Chem.Lett. Volume: 40 Pages: 744-746
  • Peer Reviewed
• [Presentation] Synthesis of Fused Heterocycles via Transition-Metal- Catalyzed Direct Annulation (2013)
  • Author(s): 佐藤哲也
  • Organizer: FLOHET-2013
  • Place of Presentation: フロリダ大学(アメリカ)
  • Year and Date: 2013-03-05
• [Presentation] Synthesis of Fused Heterocycles via Transition-metal-catalyzed Direct Annulation (2013)
  • Author(s): 佐藤 哲也
  • Organizer: FLOHET-2013
  • Place of Presentation: フロリダ大学（アメリカ）
  • Invited
• [Presentation] Chelation-Assisted Oxidative C-H Functionalization under Transition- Metal Catalysis (2012)
  • Author(s): 佐藤哲也
  • Organizer: Chemistry Seminar
  • Place of Presentation: コロンビア大学(アメリカ)
  • Year and Date: 2012-03-16
• [Presentation] Chelation-Assisted Oxidative C-H Functionalization under Transition-Metal Catalysis (2012)
  • Author(s): 佐藤 哲也
  • Organizer: 日独共同大学院プログラム シンポジウム
  • Place of Presentation: アーヘン工科大学（ドイツ）
  • Invited
• [Presentation] 遷移金属触媒を用いる芳香族基質と不飽和化合物との酸化的カップリング (2012)
  • Author(s): 佐藤 哲也
  • Organizer: 近畿化学協会有機金属部会平成23年度第4回例会
  • Place of Presentation: 大阪科学技術センター（大阪府）
  • Invited
• [Presentation] Chelation-Assisted Oxidative C-H Functionalization under Transition-Metal Catalysis (2012)
  • Author(s): 佐藤 哲也
  • Organizer: Chemistry Seminar
  • Place of Presentation: コロンビア大学（アメリカ）
  • Invited
• [Presentation] Transition-Metal-Catalyzed Oxidative Coupling of Aromatic Substrates with Unsaturated Compounds (2011)
  • Author(s): 佐藤哲也
  • Organizer: ISOMC 2011
  • Place of Presentation: 大阪大学
  • Year and Date: 2011-11-12
• [Presentation] Transition-metal-catalyzed oxidative coupling of aromatic substrates with alkynes through regioselective C-H bond cleavage (2011)
  • Author(s): 佐藤哲也
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川県)(招待講演)
  • Year and Date: 2011-03-28
• [Presentation] 炭素-水素あるいは炭素-炭素結合切断を経るカルボン酸類の触媒的カップリング反応 (2011)
  • Author(s): 佐藤哲也
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川県)(招待講演)
  • Year and Date: 2011-03-27
• [Presentation] Synthesis of Fused Aromatic- and Heteroaromatic Compounds via Transition-Metal-Catalyzed Oxidative Coupling (2011)
  • Author(s): 佐藤 哲也
  • Organizer: OMCOS-16
  • Place of Presentation: 上海国際会議場（中国）
• [Presentation] オルトメタル化を鍵とする芳香族基質と不飽和化合物との直接カップリング (2011)
  • Author(s): 佐藤 哲也
  • Organizer: 第5回物質科学フロンティアセミナー
  • Place of Presentation: 名古屋大学（愛知県）
  • Invited
• [Presentation] Transition-Metal-Catalyzed Oxidative Coupling of Aromatic Substrates with Unsaturated Compounds (2011)
  • Author(s): 佐藤 哲也
  • Organizer: ISOMC 2011
  • Place of Presentation: 大阪大学（大阪府）
  • Invited
• [Presentation] Transition metal-catalyzed oxidative coupling of aromatic substrates with alkynes and alkenes via C-H and/or C-C bond cleavage (2010)
  • Author(s): 佐藤哲也
  • Organizer: Pacifichem 2010
  • Place of Presentation: アメリカ合衆国・ホノルル
  • Year and Date: 2010-12-19
• [Presentation] Palladium-catalyzed decarboxylative coupling of biomass-derived cinnamic acids (2010)
  • Author(s): 佐藤哲也
  • Organizer: Pacifichem 2010
  • Place of Presentation: 米国・ホノルル
  • Year and Date: 2010-12-17
• [Presentation] Synthesis of Fused Aromatic Compounds via Transition-Metal-Catalyzed Oxidative Coupling (2010)
  • Author(s): 佐藤哲也
  • Organizer: 12^<th> Belgian Organic Synthesis Symposuim (BOSS-12)
  • Place of Presentation: ベルギー・ナミュール
  • Year and Date: 2010-07-12
• [Book] Transition-Metal-Mediated Aromatic Ring Construction (2013)
  • Author(s): 佐藤哲也、John Wiley and Sons
• [Book] Metal-Catalyzed Single Bond Construction (2013)
  • Author(s): 佐藤哲也
  • Publisher: Wiley-VCH
• [Book] Transition-Metal-Mediated Aromatic Ring Construction (2013)
  • Author(s): 佐藤 哲也
  • Publisher: John Wiley and Sons
• [Book] Metal-Catalyzed Single Bond Construction (2013)
  • Author(s): 佐藤 哲也
  • Publisher: Wiley-VCH
• [Book] 不活性結合・不活性分子の活性化 (2011)
  • Author(s): 佐藤 哲也
  • Publisher: 化学同人