New Synthetic Method of Polyacene Frameworks using Pyrylium Salt as a Key Intermediate

• Project/Area Number: 18350091
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials/Devices
• Research Institution: Tohoku University
• Principal Investigator: ASAO Naoki Tohoku University, 大学院・理学研究科, 准教授 (60241519)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥17,420,000 (Direct Cost: ¥14,900,000、Indirect Cost: ¥2,520,000); Fiscal Year 2008: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2007: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2006: ¥6,500,000 (Direct Cost: ¥6,500,000)
• Keywords: 有機電子材料 / ポリアセン / 芳香環形成反応 / ルイス酸触媒 / ピリリウム型中間体 / 芳香環化反応 / 塩化銅 / テトラセン / アントラセン / ベンザイン / 金触媒

Research Abstract

金触媒を用いることにより、オルトアルキニル(オキソ)ベンゼン化合物とベンザイン前駆体から、一挙に9位にケトン官能基を有するアントラセン化合物を構築する手法を見い出した。また、塩化銅を用いることにより、オルトアルキニル(オキソ)ベンゼン化合物とアセチレン化合物とから、α位にクロロ基が導入されたナフタレン化合物を一挙に構築できることを見い出した。本手法を用いることにより、テトラセン骨格の簡便な合成ルートの開発に成功した。

Research Products

• [Journal Article] Gold-catalyzed substitution reaction with ortho-alkynylbenzoic acid alkyl esters as an efficient alkylating agent (2009)
  • Author(s): Aikawa, H. ; Tago, S. ; Umetsu, K. ; Haginiwa, N. ; Asao, N.
  • Journal Title: Tetrahedron 65 Pages: 1774-1784
  • Peer Reviewed
• [Journal Article] Gold-catalyzed transesterification of ortho-alkynylbenzoic acid esters: a novel protecting group for alcohols and phenols (2008)
  • Author(s): Umetsu, K., Asao, N.
  • Journal Title: Tetrahedron Lett. 49 Pages: 7046-7049
  • Peer Reviewed
• [Journal Article] Silver-catalyzed synthesis of 1,2-dihydroisoquinolines through direct addition of carbon pronucleophiles to ortho-alkynyl aldimines (2008)
  • Author(s): Asao, N., Yudha, S. S., Nogami, T., Yamamoto, Y.
  • Journal Title: Heterocycles 76 Pages: 471-483
  • Peer Reviewed
• [Journal Article] An efficient method for construction of tetrahydroisoquinoline skeleton via double cyclization process using ortho-vinylbenzaldehydes and amino alcohols : Application to the synthesis of(S)-cryptostyline II (2008)
  • Author(s): Umetsu, K., Asao, N.
  • Journal Title: Tetrahedron Lett. 49 Pages: 2722-2725
  • Peer Reviewed
• [Journal Article] Preparation of 1,2-Dihydroxyisoquinolines by Three Component Reaction under Catalyst-Free Conditions (2008)
  • Author(s): Iso, K. Yudha S., S., Asao, N.
  • Journal Title: Synthesis 2008 Pages: 820-822
  • Peer Reviewed
• [Journal Article] AuCl-catalyzed reaction of ortho-alkynyl(oxo)benzene with benzenediazonium 2-carboxylate as a synthetic method of anthracene, triptycene, and phthalazine derivatives (2008)
  • Author(s): Sato, K., Menggenbateer, Kubota, T., Asao, N.
  • Journal Title: Tetrahedron 64 Pages: 787-796
  • Peer Reviewed
• [Journal Article] Preparation of 1, 2-Dihydroxyisoquinolines by Three Componet Reaction under Catalyst-Free Conditions (2008)
  • Author(s): Iso, K. Yudha S., S. ; Asao, N.
  • Journal Title: Synthesis Pages: 820-822
  • Peer Reviewed
• [Journal Article] An efficient method for construction of tetrahydroisoquinoline skeleton via double cyclization process using ortho-vinylbenzaldehydes and amino alcohols : Application to the synthesis of (S)-cryptostyline II (2008)
  • Author(s): Umetsu, K. ; Asao, N.
  • Journal Title: Tetrahedron Lett. 49 Pages: 2722-2725
  • Peer Reviewed
• [Journal Article] Silver-catalyzed synthesis of 1, 2-dihydroisoquinolines through direct addition of carbon pronucleophiles to ortho-alkynyl aldimines (2008)
  • Author(s): Asao, N. ; Yudha, S. S. ; Nogami, T. ; Yamamoto, Y.
  • Journal Title: Heterocycles 76 Pages: 471-483
  • Peer Reviewed
• [Journal Article] Gold-catalyzed transesterification of ortho-alkynylbenzoic acid esters : a novel protecting group for alcohols and phenols (2008)
  • Author(s): Umetsu, K. ; Asao, N.
  • Journal Title: Tetrahedron Lett. 49 Pages: 7046-7049
  • Peer Reviewed
• [Journal Article] AuCl-catalyzed reaction of ortho-alkynyl(oxo)benzene with benzenediazonium 2-carboxylate as a synthetic method of anthracene,triptycene, and phthalazine derivatives (2008)
  • Author(s): Sato, K.; Menggenbateer; Kubota, T.; Asao, N.
  • Journal Title: Tetrahedron 64 Pages: 787-796
  • Peer Reviewed
• [Journal Article] A facile synthesis of 1,2-dihydroisoquinolines by three-component reaction (2007)
  • Author(s): Iso, K., Yudha S., S., Menggenbateer, Asao, N.
  • Journal Title: Heterocycles 74 Pages: 649-660
  • Peer Reviewed
• [Journal Article] Gold-Catalyzed Etherification and Friedel-Crafts Alkylation using ortho-Alkynylbenzoic Acid Alkyl Ester as an Efficient Alkylating Agent (2007)
  • Author(s): Asao, N., Aikawa, H., Tago, S., Umetsu, K.
  • Journal Title: Org. Lett. 9 Pages: 4299-4302
  • Peer Reviewed
• [Journal Article] Gold-Catalyzed Benzannulation (2007)
  • Author(s): Asao, N., Sato, K.
  • Journal Title: J. Syn. Org. Chem. Jpn. 65 Pages: 897-904
  • NAID: 10019753136
• [Journal Article] Gold-Catalyzed Benzannulation (2007)
  • Author(s): Asao, N.; Sato, K.
  • Journal Title: J. Syn. Org. Chem. Jpn. 65 Pages: 897-904
  • NAID: 10019753136
  • Peer Reviewed
• [Journal Article] Sato, K. AuCl-Catalyzed [4+2] Benzannulation between ortho-Alkynyl(oxo)benzene and Benzyne (2006)
  • Author(s): Asao, N.
  • Journal Title: Org. Lett. 8 Pages: 5361-5363
  • Peer Reviewed
• [Journal Article] Iso, K. Yudha S., S. An Environmentally Friendly Synthetic Method of 1,2-Dihydroisoquinoline Frameworks via Three Component Reaction using ortho-Alkynylbenzaldehydes, Primary Amines, and Pronucleophiles (2006)
  • Author(s): Asao, N.
  • Journal Title: Org. Lett. 8 Pages: 4149-4151
  • Peer Reviewed
• [Journal Article] Gold- and Copper-Catalyzed [4+2] Benzannulations between Enynal or Enynone Units and 2π-Systems (2006)
  • Author(s): Asao, N.
  • Journal Title: Synlett Pages: 1645-1656
  • Peer Reviewed
• [Journal Article] Aikawa, H. Lewis Acid-Catalyzed [4+2] Benzannulation between Enynal Units and Enols or Enol Ethers: Novel Synthetic Tools for Poly-substituted Aromatic Compounds including Indole and Benzofuran Derivatives (2006)
  • Author(s): Asao, N.
  • Journal Title: J. Org. Chem. 71 Pages: 5249-5253
  • Peer Reviewed
• [Journal Article] AuCl-Catalyzed [4+2] Benzannulation between o-Alkynyl (oxo) benzene and Benzyne (2006)
  • Author(s): Naoki Asao, Kenichiro Sato
  • Journal Title: Organic Letters 8 Pages: 5361-5363
• [Journal Article] Gold-catalyzed substitution reaction with ortho-alkynylbenzoic acid alkyl esters as an efficient alkylating agent
  • Author(s): Aikawa, H., Tago, S., Umetsu, K., Haginiwa, N., Asao, N.
  • Journal Title: Tetrahedron 2009 65 Pages: 1774-1784
  • Peer Reviewed
• [Presentation] Development of new organic transformations with gold catalysts (2009)
  • Author(s): Asao, N.
  • Organizer: Joint Research Seminar of Tohoku University and University of York
  • Place of Presentation: Sendai (Japan) (Invited Lecture)
  • Year and Date: 2009-01-20
• [Presentation] Development of new organic transformations with gold catalysts (2009)
  • Author(s): Naoki Asao
  • Organizer: Joint Research Seminar of Tohoku University and University of York
  • Place of Presentation: Sendai
  • Year and Date: 2009-01-20
• [Presentation] 金触媒を用いた新規環拡大反応の開発 (2009)
  • Author(s): 久保田俊彦、浅尾直樹
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学(船橋)
• [Presentation] 金触媒を用いたアルコールの新規脱水反応の開発 (2009)
  • Author(s): 梅津和照、浅尾直樹
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学(船橋)
• [Presentation] 均一系金触媒を用いた高効率分子変換プロセスの開発 (2008)
  • Author(s): 浅尾直樹
  • Organizer: 平成20年度化学系学協会東北大会
  • Place of Presentation: 八戸工業大学(八戸)(招待講演)
• [Presentation] Gold-catalyzed α-alkylation of silyl enol ethers (2008)
  • Author(s): Asao, N.,Aikawa, H., Kaneko, T
  • Organizer: 23rd International Conference on Organometallic Chemistry(ICOMC2008)
  • Place of Presentation: Rennes (France)
• [Presentation] Novel Nucleophilic Substitution Reaction Based on the Gold-Catalyzed Formation of Leaving Group (2008)
  • Author(s): Aikawa, H., Asao, N.
  • Organizer: 17th International Conference on Organic Synthesis(ICOS 17)
  • Place of Presentation: Daejeon(Korea)
• [Presentation] 炭素親和性ルイス酸触媒によるシリルエノールエーテルのアルキル化反応の開発 (2008)
  • Author(s): 相川春夫、浅尾直樹
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学(池袋)
• [Presentation] 金触媒による加溶媒分解を機軸とする新規保護基の開発 (2008)
  • Author(s): 梅津和照、浅尾直樹
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学(池袋)
• [Presentation] Novel Nucleophilic Substitution Reaction Based on the Gold-Catalvzed Formation of Leaving Group (2008)
  • Author(s): H. Aikawa, N. Asao
  • Organizer: 17th International Conference on Organic Synthes is (ICOS 17)
  • Place of Presentation: Daejeon(Korea)
• [Presentation] Gold-catalyzed a-alkylation of silyl enol ethers (2008)
  • Author(s): N. Asao, H. Aikawa, T. Kaneko
  • Organizer: 23rd International Conference on Organometallic Chemistry (ICOMC2008)
  • Place of Presentation: Rennes(France)
• [Presentation] 均一系金触媒を用いた高効率分子変換プロセスの開発 (2008)
  • Author(s): 浅尾直樹
  • Organizer: 平成20年度化学系学協会東北大会
  • Place of Presentation: 八戸工業大学(八戸)
• [Presentation] Gold-Catalyzed Etherification of Alcohols with 2-Alkynylbenzoic Acid Alkyl Esters (2007)
  • Author(s): Asao, N.
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007
  • Place of Presentation: Singapore(Invited Lecture)
  • Year and Date: 2007-12-17
• [Presentation] Gold-Catalyzed Etherification of Alcohols with 2-Alkynylbenzoic Acid Alkyl Esters (2007)
  • Author(s): Asao, N.
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007
  • Place of Presentation: シンガポール
  • Year and Date: 2007-12-17
• [Presentation] Gold-Catalyzed Etherification by Nucleophilic Substitution of ortho-Alkynylbenzoic Acid Esters with Alcohols (2007)
  • Author(s): Asao, N
  • Organizer: 14^th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: Nara(Japan)
  • Year and Date: 2007-08-05
• [Presentation] Gold-Catalyzed Etherification by Nucleophilic Substitution of ortho-Alkynylbenzoic Acid Esters with Alcohols (2007)
  • Author(s): Asao, N.
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: 奈良
  • Year and Date: 2007-08-05
• [Presentation] Gold-Catalyzed Etherification and Friedel-Crafts Alkylation Using ortho-Alkynylbenzoic Acid Esters (2007)
  • Author(s): Asao, N., Aikawa, H., Tago, S
  • Organizer: 第54回有機金属化学討論会
  • Place of Presentation: 広島大学(広島)
• [Presentation] 金触媒を用いた脱離基形成による新規求核置換反応の開発 (2007)
  • Author(s): 相川春夫、浅尾直樹
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学(大阪)
• [Presentation] 金触媒によるジアゾニウム化合物を用いた新規環化反応の開発 (2007)
  • Author(s): 佐藤健一郎、久保田俊彦、浅尾直樹
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学(大阪)
• [Presentation] 三成分連結反応による1, 2-ジヒドロイソキノリン骨格の自己形成 (2007)
  • Author(s): 磯健太郎、Yudha, S.S.、梅津和照、浅尾直樹
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学(大阪)
• [Presentation] ドミノ型分子内閉環反応によるテトラヒドロイソキノリン骨格の新規不斉合成法の開発 (2007)
  • Author(s): 梅津和照、浅尾直樹
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学(大阪)
• [Presentation] パラジウム触媒による分子内イミノエン反応の開発 (2007)
  • Author(s): 磯貝幸枝、田子咲恵、Yudha, S.S.、浅尾直樹
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学(大阪)
• [Presentation] New Synthetic Methods for 1,2-Dihydroisoquinolines and Tetrahydroisoquinolines Derivatives Utilizing Silver and Rhodium Catalysts (2006)
  • Author(s): Yudha, S.S.、Asao, N.、Yamamoto, Y
  • Organizer: 7th Tetrahedron Symposium
  • Place of Presentation: Kyoto (Japan)
• [Presentation] Synthesis of Angucyclinone Antibiotic via Gold-Catalyzed Intramolecular [4+2] Benzannulation (2006)
  • Author(s): Sato, K., Asao, N., Yamamoto, Y
  • Organizer: 7th Tetrahedron Symposium
  • Place of Presentation: Kyoto(Japan)
• [Remarks] Asao, N. Development of New Organic Transformations with Gold Catalysts, 2008年11月18日, Paris (France)
• [Remarks] Asao, N. Development of New Organic Transformations with Gold Catalysts, 2008年11月12日, Nantes (France)
• [Remarks] Asao, N. Development of New Organic Transformations with Gold Catalysts, 2008年11月11日, Rennes (France)
• [Remarks] Asao, N. Development of New Organic Transformations with Coinage Metal Catalysts, 2008年7月11日, Rouen(France)