Synthesis of linear and branched oligomers with the coupling reaction of heteroaromatic compounds

• Project/Area Number: 25288049
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kobe University
• Principal Investigator: Mori Atsunori 神戸大学, 工学(系)研究科(研究院), 教授 (90210111)
• Co-Investigator(Renkei-kenkyūsha): UEDA Yasukiyo 神戸大学, 大学院・工学研究科, 教授 (40116190) ; SUGIE Atsushi 神戸大学, 大学院・工学研究科, 助教 (80605907)
• Project Period (FY): 2013-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥18,330,000 (Direct Cost: ¥14,100,000、Indirect Cost: ¥4,230,000); Fiscal Year 2016: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2015: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2013: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000)
• Keywords: ヘテロ芳香族化合物 / 分岐状オリゴマー / 鎖状オリゴマー / Ｃ－Ｈカップリング / 遷移金属触媒 / ヘテロ芳香族 / オリゴチオフェン / ポリチオフェン / カップリング反応 / チオフェン / チエニレンビニレン / 溝呂木－Heck型反応 / C-Hカップリング / チエニレン－ビニレン / N-ヘテロ環状カルベン / シロキサン結合 / デンドリマー / ニッケル触媒 / 色素増感太陽電池 / カルバゾール / シアノアクリル酸 / 有機色素 / CHカップリング / 分岐状チオフェン / 太陽電池

Outline of Final Research Achievements

Linear and branched heteroaromatic oligomers were synthesized using C-H coupling reactions catalyzed by transition metal complexes, in which tolerance of various functional groups were studied. Further functional group transformation reactions were developed to undergo additional extension of the heteroaromatic unit. Disiloxane moieties was successfully introduced into olikgothiophenes to improve solubilities towared organic solvents. Water-soluble group was also examined to introduce as a functional group. Heteroaromatic oligomers bearing vinylene spacer were also prepared.

Research Products

• [Journal Article] Remarkable Reactivity Difference of Chlorothiophene vs. Chlorinated Oligothiophenes in the NiCl2(PPh3)2-Catalyzed Polymerization (2017)
  • Author(s): 中川 尚希，小倉 忠之，藤田 佳祐，炭野 有吾，橋本 亨昌，岡野 健太郎，森 敦紀
  • Journal Title: Chem. Lett. Volume: 46 Issue: 4 Pages: 453-455
  • DOI: 10.1246/cl.161180
  • NAID: 130005549099
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Step-Efficient Pathway to Chlorine-Functionalized Thiophene Oligomers by Palladium-Catalyzed Deprotonative Coupling of Chlorothiophenes (2017)
  • Author(s): 藤田 佳祐，中川 尚希，砂原 一潤，小倉 忠之，岡野 健太郎，森 敦紀
  • Journal Title: Synthesis Volume: 49 Issue: 06 Pages: 1285-1294
  • DOI: 10.1055/s-0036-1588094
  • NAID: 120006220755
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Poly(3-substituted thiophene)s of Remarkably High Solubility in Hydrocarbon via Nickel-Catalyzed Deprotonative Cross-Coupling Polycondensation (2016)
  • Author(s): 3.Fujita, K.; Sumino, Y.; Ide, K.; Tamba, S.; Shono, K.; Shen, J.; Nishino, T.; Mori, A.*; Yasuda, T.
  • Journal Title: Macromolecules Volume: 49 Issue: 4 Pages: 1259-1269
  • DOI: 10.1021/acs.macromol.5b02524
  • Peer Reviewed
• [Journal Article] Synthesis of Oligo(thienylene-vinylene) by Regiocontrolled Deprotonative Cross Coupling (2016)
  • Author(s): Shota Tanaka, Yuta Fukui, Naoki Nakagawa, Kohei Murakami, Takurou N. Murakami, Nagatoshi Koumura, Atsunori Mori
  • Journal Title: Organic Letters Volume: 2016 Issue: 4 Pages: 650-653
  • DOI: 10.1021/acs.orglett.5b03567
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Furan-Oxazole Conjugated Fluorescent Materials from Biomass-Derived Furfural through Cross-Coupling Reactions (2016)
  • Author(s): Y. Murase, K. Ashida, S. Tanaka, K. Okano, A. Mori
  • Journal Title: Heterocycles Volume: 93 Issue: 1 Pages: 140-140
  • DOI: 10.3987/com-15-s(t)9
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Linear-selective Cross-coupling Polymerization of Branched Oligothiophene by Deprotonative Metalation and Cross-coupling (2015)
  • Author(s): Kohei Murakami, Shota Tanaka, Atsunori Mori
  • Journal Title: Polymer Chem/ Volume: 6 Issue: 36 Pages: 6573-6578
  • DOI: 10.1039/c5py00945f
  • NAID: 120006220765
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Addition-Elimination of Aryldimethylaluminum to Vinylarenes Promoted by the Addition of Ketone (2015)
  • Author(s): Kazuki Itami, Shota Tanaka, Kazuhiro Sunahara, Go Tatsuta, Atsunori Mori
  • Journal Title: Asian J. Org. Chem. Volume: 6 Pages: 6573-6578
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantioselective Synthesis of Macrocyclic Heterobiaryl Derivatives of Molecular Asymmetry by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis (2015)
  • Author(s): Yoichi Okayama, Satoru Tsuji, Yuka Toyomori, Atsunori Mori, Sachie Arae, Wei-Yi Wu, Tamotsu Takahashi, Masamichi Ogasawara
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54
  • NAID: 120006220759
  • Peer Reviewed
• [Journal Article] Ethylaluminum as an ethylene source for the Mizoroki-Heck-type reaction. Rhodium-catalyzed preparation of stilbene derivatives (2015)
  • Author(s): Shota Tanaka, Kazuki Itami, Kazuhiro Sunahara, Go Tatsuta, Atsunori Mori
  • Journal Title: Chemical Communications Volume: 51 Issue: 10 Pages: 1949-1952
  • DOI: 10.1039/c4cc09306b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Palladium-Catalyzed α-Arylation of Carboxylic Acid Derivatives with Grignard Reagent (2014)
  • Author(s): Daiki Tanaka, Shota Tanaka, Atsunori Mori
  • Journal Title: European Journal of Organic Chemistry Volume: 2014 Issue: 20 Pages: 4254-4257
  • DOI: 10.1002/ejoc.201402450
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Polythiophene synthesis via halogen dance (2014)
  • Author(s): Keisuke Shono, Yugo Sumino, Shota Tanaka, Shunsuke Tamba, Atsunori Mori
  • Journal Title: Organic Chemistry Frontiers Volume: 1 Issue: 6 Pages: 678-682
  • DOI: 10.1039/c4qo00109e
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Studies on the effect of N-heterocyclic carbene as a ligand for nickel(II)-catalyzed polymerization of thiophenes (2014)
  • Author(s): Atsunori Mori, Makoto Fujio, Shunsuke Tamba
  • Journal Title: Heterocycles Volume: 90 Issue: 1 Pages: 617-617
  • DOI: 10.3987/com-14-s(k)11
  • NAID: 120006220734
  • Peer Reviewed
• [Journal Article] Synthesis and properties of regioregular poly (3-substituted thiophene) bearing disiloxane moiety in the substituent. Remarkably high solubility in hexane. (2014)
  • Author(s): Atsunori Mori, Kenji Ide, Shunsuke Tamba, Satoru Tsuji, Yuka Toyomori, Takeshi Yasuda.
  • Journal Title: Chemistry Letters Volume: 43 Issue: 5 Pages: 640-642
  • DOI: 10.1246/cl.131222
  • NAID: 130004868129
  • Peer Reviewed
• [Journal Article] Nickel(II)-Catalyzed Cross-Coupling Pelycondensation of Thiophones via C-S Bond Cleavage (2014)
  • Author(s): Shunsuke Tamba, Kanta Fuji, Karin Nakamura, Atsunori Mori
  • Journal Title: Organometallics Volume: 33 Issue: 1 Pages: 12-15
  • DOI: 10.1021/om4010737
  • Peer Reviewed
• [Journal Article] Introduction of Heteroarene Functionality on the Bipedal-Thiol-Capped Gold Nanoparticle by Deprotonative C-H Coupling with Palladium Complex (2014)
  • Author(s): Atsuahi Sugie, Hiroki Yamauchi, Kei, Miyamura, Kenta Kumazawa, Shota Tanaka, Kiyoshi Kanie, Atsushi Muramatsu, Atsunori Mori
  • Journal Title: Heterocycles Volume: Vol 88, No.1 Issue: 1 Pages: 213-221
  • DOI: 10.3987/com-13-s(s)1
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Cross-Coupling of Vinylarenes with Arylaluminum Reagents in the Presence of Ketones (2014)
  • Author(s): Shota Tanaka, Atsunori Mori
  • Journal Title: European Journal of Organic Chemistry Volume: Vbl.2014,Issue6 Issue: 6 Pages: 1167-1171
  • DOI: 10.1002/ejoc.201301757
  • Peer Reviewed
• [Journal Article] Murahashi Coupling Polymerization : Nickel(II)-N-Hererocyclic Carbene Complex-Catalyzed Polycondensation of Organolithium Species of (Hetero) arenes (2013)
  • Author(s): Kanta Fuii, Shunsuke Tamba, Keisuke Shono, Atsushi Sugie, Atsunori Mori
  • Journal Title: Journal of the American Chemical Society Volume: 135 Issue: 33 Pages: 12208-12211
  • DOI: 10.1021/ja406374t
  • Peer Reviewed
• [Journal Article] Facile Preparation of Poly(3-Substituted Thiophene) Block Copolymers by Nickel-catalyzed Deprotonative Polycondensation without External Generation of Thiophene Organometallic Species (2013)
  • Author(s): Karin Nakamura, Shunsuke Tamba, Atsushi Sugie, Atsunori Mori
  • Journal Title: Chemistry Letters Volume: 40 Issue: 10 Pages: 1200-1202
  • DOI: 10.1246/cl.130523
  • NAID: 10031201309
  • Peer Reviewed
• [Journal Article] Deprotonative metalation of chlorothiophene with Grignard reagent and catalytic cis-2, 6-dimethylpiperidine under mild conditions (2013)
  • Author(s): Shunsuke Tamba. Kenji Ide, Keisuke Shono, Atsushi Sugie, Atsunori Mori
  • Journal Title: Synlett Volume: (印刷中)(掲載確定) Issue: 09 Pages: 1133-1136
  • DOI: 10.1055/s-0033-1338385
  • Peer Reviewed
• [Journal Article] Studies on the preference of multiple coupling in the introduction of thiophene ring into poly-halogenated aromatic compounds with nickel NHC catalyst (2013)
  • Author(s): Shota Tanaka
  • Journal Title: Tetrahedron Letters Volume: 54 Issue: 15 Pages: 1976-1979
  • DOI: 10.1016/j.tetlet.2013.01.127
  • Peer Reviewed
• [Presentation] 閉環メタセシス反応を用いないつるまき状分子不斉を有する新規大環状へテロアリールの合成 (2017)
  • Author(s): 芦田 汐未，田中 直樹，岡野 健太郎，森 敦紀
  • Organizer: 日本化学会第９７春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] 縮合反応を経由する非対称型つるまき状分子不斉化合物の合成 (2017)
  • Author(s): 井上 僚，松岡 大地，丸橋 和希，芦田 汐未，岡野 健太郎，森 敦紀
  • Organizer: 日本化学会第９７春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] ベンゾオキサゾールを配向基とするブロモフランのハロゲンダンス (2017)
  • Author(s): 宮川 直樹，村瀬 右樹，岡野 健太郎，森 敦紀
  • Organizer: 日本化学会第９７春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] つる巻き状分子不斉の創出 (2016)
  • Author(s): 森 敦紀
  • Organizer: 平成28年度有機合成化学北陸セミナー
  • Place of Presentation: 石川県青少年総合研修センター（石川県・金沢市）
  • Year and Date: 2016-10-07
  • Invited
• [Presentation] Heterobiaryl with winding-vine-shaped molecular asymmetry (2016)
  • Author(s): 森 敦紀
  • Organizer: INTERNATIONAL SYMPOSIUM ON PURE & APPLIED CHEMISTRY (ISPAC) 2016
  • Place of Presentation: クチン（マレーシア）
  • Year and Date: 2016-08-15
  • Invited
• [Presentation] 炭素－塩素結合をもつチオフェン誘導体のC-H結合におけるカップリング反応によるチオフェン－チオフェン結合の生成 (2016)
  • Author(s): 藤田佳佑・中川直希・砂原一潤・岡野健太郎・森敦紀
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学（京都府，京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] チオフェン誘導体のC-Hカップリング重合におけるモノマー構造多様性の検討 (2016)
  • Author(s): 中川直希・小倉忠之・藤田佳佑・炭野有吾・福井祐太・田中将太・岡野健太郎・森敦紀
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学（京都府，京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] チオフェン誘導体のC-Hカップリング重合における配位子効果の検討 (2016)
  • Author(s): 小倉忠之・中川直希・藤尾慎・橋本享昌・岡野健太郎・森敦紀
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 同志社大学（京都府，京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] 側鎖にジシロキサン結合を有する高脂溶性ポリチオフェンの合成 (2015)
  • Author(s): 炭野有吾・井手賢治・藤田佳佑・森 敦紀
  • Organizer: 第61回高分子研究発表会（神戸）
  • Place of Presentation: 神戸県民会館（兵庫県，神戸市）
  • Year and Date: 2015-07-17
• [Presentation] Development on the Preparative Method for Oligothiophenes and Polythiophenes with Well-defined Structures (2014)
  • Author(s): Atsunori Mori
  • Organizer: Vietnam-Malaysia International Chemical Congress
  • Place of Presentation: ベトナム，ハノイ
  • Year and Date: 2014-11-07 – 2014-11-09
  • Invited
• [Presentation] アリールアルミニウムのビニルアレーンへの溝呂木-Heck型付加脱離反応 (2014)
  • Author(s): 伊丹一起・田中将太・砂原一潤・立田 豪・森 敦紀
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学
  • Year and Date: 2014-09-23 – 2014-09-25
• [Presentation] Head to tail型チエニレン-ビニレンオリゴマーの精密合成 (2014)
  • Author(s): 福井祐太・田中将太・中川直希・森 敦紀
  • Organizer: 福井祐太・田中将太・中川直希・森 敦紀
  • Place of Presentation: 東北大学
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] ニッケル触媒を用いたポリチオフェン合成におけるN-ヘテロ環状カルベン(NHC)配位子効果の検討 (2014)
  • Author(s): 村上航平・森 敦紀
  • Organizer: 有機合成若手セミナー
  • Place of Presentation: 大阪大学
  • Year and Date: 2014-08-05
• [Presentation] ハロゲンダンスを利用したポリチオフェン合成法 (2014)
  • Author(s): 炭野有吾，庄野圭亮，田中将太，丹波俊輔，森 敦紀
  • Organizer: 第60回高分子研究発表会（神戸）
  • Place of Presentation: 神戸市
  • Year and Date: 2014-07-24 – 2014-07-25
• [Presentation] フルフラールを用いたπ共役系が拡張し たヘテロ芳香族化合物の合成 (2014)
  • Author(s): 立田 豪・田中将太・杉江敦司・森 敦紀
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] 3 位置換基にジシロキサン結合を有する head-to-tail 型ポリチオフェンの 合成と性質 (2014)
  • Author(s): 豊森佑夏・井手賢治・丹波俊輔・辻 悟・森 敦紀
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] 位置選択的なCｰHカップリングを用いる 構造が明確に制御されたチエニレン－ビ ニレンオリゴマーの新規合成法 (2014)
  • Author(s): 福井 祐太・田中 将太・森 敦紀
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] オリゴチオフェンデンドリマーをモノマ ーとして用いる直鎖状高分子の合成 (2014)
  • Author(s): 村上航平，田中将太，森 敦紀
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] ロジウム触媒を用いたアリールアルミニ ウムのビニルアレーンへの付加脱離反応 (2014)
  • Author(s): 田中 将太・伊丹 一起・立田 豪・森 敦紀
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] ヘテロ芳香族の触媒的Ｃ－Ｈカップリング :チオフェン系有機材料,高分子材料の実用的合成法をめざして (2014)
  • Author(s): 森 敦紀
  • Organizer: 有機合成化学協会関西支部2月セミナー
  • Place of Presentation: 大阪科学技術センター
  • Invited
• [Presentation] 触媒的C-Hカップリング反応を活用する有機合成，高分子合成 (2014)
  • Author(s): 森 敦紀
  • Organizer: 有機合成化学協会後期（秋季）有機合成講習会
  • Place of Presentation: 日本薬学会長井記念館
  • Invited
• [Presentation] Rhodium-Catalyzed Mizoroki-Heck Reaction of Arylaluminum with Vinylarene (2013)
  • Author(s): Shota Tanaka, Atsunori Mori
  • Organizer: 第10回カルボアニオン化学国際会議
  • Place of Presentation: 同志社大学
• [Presentation] パラジウム触媒を用いるα-アリールカルボン酸とハロゲン化アリールとのクロスカップリング反応 (2013)
  • Author(s): 田中大貴，田中将太，杉江敦司，森 敦紀
  • Organizer: 有機金属討論会
  • Place of Presentation: 学習院大学
• [Presentation] Iterative synthesis of well-defined linear and branched oligothiophenes by nickel-catalyzed regioselective cross coupling (2013)
  • Author(s): Shota Tanaka, Daiki Tanaka, Go Tatsuta, Kohei Murakami, Shunsuke Tamba, Atsushi Sugie, Atsunori Mori
  • Organizer: The 17th International Conference of Organometallic Chemistry Directed for Organic Synthesis
  • Place of Presentation: Colorado State University （アメリカ）
• [Remarks] 研究の概要
  • URL: http://seesaawiki.jp/w/moriorg3/d/Topics?wiki_id=45657
• [Remarks] 研究トピックス
  • URL: http://seesaawiki.jp/w/moriorg3/d/Topics?wiki_id=45657
• [Patent(Industrial Property Rights)] フランオリゴマーポリエステルおよびその前駆体 (2017)
  • Inventor(s): 森 敦紀，宮川 直樹，岡野 健太郎，松本 拓也
  • Industrial Property Rights Holder: 森 敦紀，宮川 直樹，岡野 健太郎，松本 拓也
  • Industrial Property Rights Type: 特許
  • Filing Date: 2017-03-10
• [Patent(Industrial Property Rights)] 五員ヘテロアリーレン－ビニレンポリマーの製造方法 (2015)
  • Inventor(s): 森 敦紀
  • Industrial Property Rights Holder: 森 敦紀
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2015-001160
  • Filing Date: 2015-01-30