Generation of Novel Aromatic Compounds by Controlled Reactions of Accumulated Alkynes

2013 Fiscal Year Final Research Report

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 21106011
• 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: TOBE Yoshito 大阪大学, 基礎工学研究科, 教授 (60127264)
• Co-Investigator(Kenkyū-buntansha): TAHARA Kazukuni 大阪大学, 大学院基礎工学研究科, 助教 (40432463) ; UMEDA Rui 関西大学, 工学部, 准教授 (70467512)
• Project Period (FY): 2009-07-23 – 2014-03-31
• Keywords: 反応集積化 / 渡環環化反応 / 芳香族化合物 / インデノフルオレン / 一重項ビラジカル / シクロオクタテトラエン

Research Abstract

On the basis of the concept of "space-and-time-integration," we developed a methodology to synthesize selectively and effciently aromatic compounds, which are difficult to obtain by conventional synthetic methods, having novel structures and electronic properties by transannular and/or tandem cyclization reactions using highly reactive acetylenic substrates having closely located alkynyl groups. In addition, the reactive intermediates generated during the course of the reactions were furhter transformed into more elaborated products in some cases. The structures, physical properties, and optoelectronic applications of newly synthesized aromatic compounds were investigated including photovoltaic applications of some products.

Research Products

• [Journal Article] Electrophilic Tandem Transannular Cyclization of Octadehydrotribenz- [14]annulenes to Benzodiindeno - cyclooctatetraenes (2014)
  • Author(s): Shunpei Nobusue, Yoshito Tobe
  • Journal Title: Chem. Lett Volume: 43 (印刷中)
  • Peer Reviewed
• [Journal Article] [4.2](2,2')(2,2')Biphenylophanetri yne: A Twisted Biphenylophane with a Highly Distorted Diacetylene Bridge (2014)
  • Author(s): Shunpei Nobusue, Hiroshi Yamane, Horokazu Miyoshi, Yoshito Tobe
  • Journal Title: Org. Lett Volume: 16 Pages: 1940-1943
  • DOI: 10.1021/ol5004934
  • Peer Reviewed
• [Journal Article] Benz[c]indeno[2,1-a]fluorene: A 2,3-Naphthoquinodimethane Incorporated into an Indenofluorene Frame (2014)
  • Author(s): Hirokazu Miyoshi, Shunpei Nobusue, Akihiro Shimizu, Ichiro Hisaki, Mikiji Miyata, Yoshito Tobe
  • Journal Title: Chem. Sci Volume: 5 Pages: 163-168
  • DOI: 10.1039/c3sc52662d
  • Peer Reviewed
• [Journal Article] Synthesis and Physical Properties of Zethrene Derivatives Bearing Donor/Acceptor Substituents at 7,14-Positions (2013)
  • Author(s): Daijiro Hibi, Kenichi Kitabayashi, Akihiro Shimizu, Rui Umeda, Yoshito Tobe
  • Journal Title: Org. Biomol. Chem Volume: 11 Pages: 8256-8261
  • DOI: 10.1039/C3OB41674G
  • Peer Reviewed
• [Journal Article] Syntheses and Properties of Graphyne Fragments: Trigonally Expanded Dehydrobenzo[12]annulenes (2013)
  • Author(s): Kazukuni Tahara, Yuki Yamamoto, Dustin E. Gross, Hiroyoshi Kozuma, Yoko Arikuma, Koji Ohta, Yoshiko Koizumi, Yuan Gao, Yo Shimizu, Shu Seki, Kenji Kamada, Jeffrey S, Moore, Yoshito Tobe
  • Journal Title: Chem. Eur. J Volume: 19 Pages: 11251-11260
  • DOI: 10.1002/chem.201300838
  • Peer Reviewed
• [Journal Article] Indeno[2,1,-b]fluorene: A 20π Electron Hydrocarbon with Very Low Energy Light Absorption (2013)
  • Author(s): Akihiro Shimizu, Ryohei Kishi, Masayoshi Nakano, Daisuke Shiomi, Kazunobu Sato, Kakeji Takui, Ichiro Hisaki, Mikiji Miyata, Yoshito Tobe
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Pages: 6076-6079
  • DOI: 10.1002/anie.201302091
  • Peer Reviewed
• [Journal Article] Oxidative Cyclodimerization that Follows Tandem Cyclization of Dehydro[14]annulenes Induced by Alkyllithium (2013)
  • Author(s): Shunpei Nobusue, Akihiro Shimizu, Kenji Hori, Ichiro Hisaki, Mikiji Miyata, Yoshito Tobe
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Pages: 4184-4188
  • DOI: 10.1002/anie.201210233
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of 1,4,5,8-Tetraethynylnaphthalene Derivatives (2012)
  • Author(s): Takashi Takeda, Yoshito Tobe
  • Journal Title: Chem. Commun Volume: 48 Pages: 7841-7843
  • DOI: 10.1039/c2cc33740a
  • Peer Reviewed
• [Journal Article] Electrophilic Transannular Cyclization of Octadehydrodibenzo[12]annulene Reexamined: Indication of the Formation of Both anti- and syn-Indenofluorenes (2011)
  • Author(s): Takashi Takeda, Koji Inukai, Kazukuni Tahara, Yoshito Tobe
  • Journal Title: J. Org. Chem Volume: 76 Pages: 9116-9121
  • DOI: 10.1021/jo2014593
  • Peer Reviewed
• [Journal Article] Indeno[2,1-a]fluorene: An Air-Stable ortho-Quinodimethane Derivatives, Angew (2011)
  • Author(s): Akihiro Shimizu, Yoshito Tobe
  • Journal Title: Chem. Int. Ed Volume: 50 Pages: 6906-6910
  • DOI: 10.1002/anie.201101950
  • Peer Reviewed
• [Journal Article] Tetradehydrodinaphtho- [10]annulene and its Transformation into Zethrene: A Hitherto Unknown Dehydroannulene and a Forgotten Aromatic Hydrocarbon (2010)
  • Author(s): Rui Umeda, Daijiro Hibi, Koji Miki, Yoshito Tobe
  • Journal Title: Pure Appl. Chem Volume: 82 Pages: 871-878
  • DOI: 10.1351/PAC-CON-09-10-12
  • Peer Reviewed
• [Presentation] 新奇な構造をもつ共役パイ電子系炭化水素の創出に関する研究 (2013)
  • Author(s): 戸部義人
  • Organizer: 第7回有機π電子系シンポジウム
  • Place of Presentation: 高崎
  • Year and Date: 20131213-14
• [Presentation] The Indenofluorene Business (2013)
  • Author(s): Yoshito Tobe
  • Organizer: 15th Asian Chemical Congress
  • Place of Presentation: Singapore, Singapore
  • Year and Date: 20130819-23
• [Presentation] Indenofluorene Congeners: Biradicaloids and Beyond (2013)
  • Author(s): Yoshito Tobe
  • Organizer: 15th International Symposium on Novel Aromatic Compounds (ISNA-15)
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 20130728-0802
• [Presentation] ゼトレンとインデノフルオレン:古くて新しい芳香族化合物の化学 (2012)
  • Author(s): 戸部義人
  • Organizer: 平成24年度有機合成化学北陸セミナー
  • Place of Presentation: 富山
  • Year and Date: 20121005-06
• [Presentation] Zethrenes and Indenofluorenes: Old yet New Aromatic Hydrocarbons with Singlet Biradical Characters (2012)
  • Author(s): Yoshito Tobe
  • Organizer: UDS-JSPS Joint Seminar
  • Place of Presentation: Strasbourg, France
  • Year and Date: 2012-06-12
• [Presentation] Transannular Approaches to Polycyclic Aromatic Hydrocarbons from Dehydrobenzoannulenes (2010)
  • Author(s): Yoshito Tobe
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 20101215-20
• [Presentation] Some Uncovered Facets in Dehydroannulene Chemistry: Reactivity, Aromaticity, and Self-Assembly on Solid Surface (2009)
  • Author(s): Yoshito Tobe
  • Organizer: The 13th International Symposium on Novel Aromatic Compounds (ISNA-13)
  • Place of Presentation: Luxembourg
  • Year and Date: 20090719-24
• [Book] Science of Synthesis; Jay S. Siegel, Yoshito Tobe, Eds.; Aromatic Ring Assemblies, Polycyclic Aromatic Hydrocarbons, and Conjugated Polyenes; Georg Thieme: Stuttgart (2010)
  • Author(s): Yoshito Tobe, Takashi Takeda
  • Total Pages: 1311-1348
• [Remarks]
  • URL: http://www.supra.chem.es.osaka-u.ac.jp/
• [Patent(Industrial Property Rights)] 光起電力素子用化合物、光起電力素子用材料および光起電力素子 (2013)
  • Inventor(s): 戸部義人、信末俊平、清水章弘、北澤大輔、山本修平
  • Industrial Property Rights Holder: 戸部義人、信末俊平、清水章弘、北澤大輔、山本修平
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 特願2013-035113
  • Filing Date: 2013-02-25