Synthesis of polypeptide by alternating copolymerization of imines with carbon monoxide

• Project/Area Number: 26620093
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Polymer chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Takeuchi Daisuke 東京工業大学, 科学技術創成研究院, 准教授 (90311662)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2016: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 触媒 / ペプチド / 共重合 / 一酸化炭素 / ポリアミド / ブタジエン / パラジウム錯体 / ポリペプチド / 複核錯体

Outline of Final Research Achievements

Synthesis of polypeptides by alternating copolymerization of imines with carbon monoxide was investigated. The reaction of phenylaldimine with carbon monoxide by mononuclear Pd complex resulted in almost no polymerization. The reaction of cinnamaldimine or cyclobutanimie with carbon monoxide afforded insoluble product or oligomeric product. Dinuclear Pd complexes and aluminum-palladium complexes were designed and utilized for the reaction, but almost no polymerization took place. Aluminum-cobalt and aluminum-nickel complexes were found to show higher catalytic activity toward the polymerization of butadiene than the corresponding mononuclear cobalt and nickel complexes.

Research Products

• [Journal Article] Ethylene polymerization catalyzed by dinickel complexes with a double-decker structure (2017)
  • Author(s): Daisuke Takeuchi, Yuriko Chiba, Shigenaga Takano, Hideo Kurihara, Minoru Kobayashi, Kohtaro Osakada
  • Journal Title: Polymer Chemistry Volume: 印刷中 Issue: 34 Pages: 5112-5119
  • DOI: 10.1039/c7py00333a
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Polystyrene Catalyzed by Monophosphine Pd Complexes (2016)
  • Author(s): Matthieu Jouffroy, Dominique Armspach, Dominique Matt, Kohtaro Osakada, Daisuke Takeuchi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Pages: 8367-8370
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Controlled isomerization polymerization of olefins, cycloolefins, and dienes (2016)
  • Author(s): Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Polymer Volume: 82 Pages: 392-405
  • DOI: 10.1016/j.polymer.2015.09.077
  • Peer Reviewed
• [Journal Article] Synthesis of Optically Active Polystyrene using Monophosphine Pd Complexes (2016)
  • Author(s): Matthieu Jouffroy, Dominique Armspach, Dominique Matt, Kohtaro Osakada, Daisuke Takeuchi
  • Journal Title: Angewandte Chemie, International Edition Volume: 55 Issue: 29 Pages: 8367-8370
  • DOI: 10.1002/anie.201603191
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Double cyclizative polymerization of trienes catalyzed by Pd complexes. Combined ring-forming and chain-walking reactions of the growing end (2015)
  • Author(s): Kenya Motokuni, Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Polymer Chemistry Volume: 6 Issue: 8 Pages: 1248-1254
  • DOI: 10.1039/c4py01555j
  • Peer Reviewed
• [Journal Article] Cyclopolymerization of 1,6-heptadienes and 1,6,11-dodecatrienes having acyclic substitutents catalyzed by Pd-diimine complexes (2015)
  • Author(s): Kenya Motokuni, Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Polymer Bulletin Volume: 72 Pages: 583-597
  • Peer Reviewed
• [Journal Article] Polymerization of Methylenecyclohexanes Catalyzed by Diimine-Pd Complex. Polymers Having trans- or cis-1,4- and trans-1,3-Cyclohexylene Groups (2015)
  • Author(s): Daisuke Takeuchi, Keisuke Watanabe, Kenji Sogo, Kohtaro Osakada
  • Journal Title: Organometallics Volume: 34 Issue: 12 Pages: 3007-3011
  • DOI: 10.1021/acs.organomet.5b00313
  • Peer Reviewed
• [Journal Article] Synthesis of Polyketones Containing substituted Six-Membered Rings via Pd-Catalyzed Copolymerization of Methylenecyclohexanes with Carbon Monoxide (2015)
  • Author(s): Daisuke Takeuchi, Keisuke Watanabe, Kohtaro Osakada
  • Journal Title: Macromolecules Volume: 48 Issue: 18 Pages: 5745-6749
  • DOI: 10.1021/acs.macromol.5b01458
  • Peer Reviewed
• [Journal Article] Olefin Polymerization Catalyzed by Double-Decker Dipalladium Complexes: Low Branched Poly(a-Olefin)s by Selective Insertion of the Monomer Molecule (2015)
  • Author(s): Shigenaga Takano, Daisuke Takeuchi, Kohtaro Osakada
  • Journal Title: Chemistry - A European Journal Volume: 21 Issue: 45 Pages: 16209-16218
  • DOI: 10.1002/chem.201501991
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Selective Formation of Ethyl- and/or Propyl-branched Oligoethylene Using Double-decker-type Dinuclear Fe Complexes as the Catalyst (2014)
  • Author(s): S. Takano, Y. Takeuchi, D. Takeuchi, K. Osakada
  • Journal Title: Chem. Lett Volume: 43 Issue: 4 Pages: 465-467
  • DOI: 10.1246/cl.131065
  • NAID: 130004868050
  • Peer Reviewed
• [Journal Article] Double Cyclopolymerization of Monoterminal Trienes Using Pd Catalysis. Polymers Containing Functionallized Cyclic Groups with a Regulated Sequence (2014)
  • Author(s): K. Motokuni, D. Takeuchi, K. Osakada
  • Journal Title: Macromolecules Volume: 47 Issue: 18 Pages: 6522-6526
  • DOI: 10.1021/ma500871f
  • Peer Reviewed
• [Journal Article] Ethylene Polymerization at High Temperatures Catalyzed by Double- Decker-Type Dinuclear Iron and Cobalt Complexes: Dimer Effect on Stability of the Catalyst and Polydispersity of the Product (2014)
  • Author(s): D. Takeuchi, S. Takano, Y. Takeuchi, K. Osakada
  • Journal Title: Organometallics Volume: 33 Issue: 19 Pages: 5316-5323
  • DOI: 10.1021/om500629a
  • Peer Reviewed
• [Journal Article] Double-Decker Type Dipalladium Catalyst for Olefin Polymerization. Introduction of Acrylate Units into Main Chain of Branched Polyethylene (2014)
  • Author(s): S. Takano, D. Takeuchi, K. Osakada, N. Akamatsu, A. Shishido
  • Journal Title: Angew. Chem. Int. Ed Volume: (印刷中) Issue: 35 Pages: 9246-9250
  • DOI: 10.1002/anie.201404339
  • Peer Reviewed
• [Presentation] Controlled Polymerization and Copolymerization of Olefins by Diimine Pd Catalysts (2016)
  • Author(s): Daisuke Takeuchi, Yuki Tokura, Keisuke Ito, Kohtaro Osakada
  • Organizer: The International Rubber Conference 2016
  • Place of Presentation: 北九州国際会議場
  • Year and Date: 2016-10-24
  • Int'l Joint Research
• [Presentation] Polymerization of 1,3-Butadiene by Iron Catalysts with Tridentate Ligands (2016)
  • Author(s): Fukutaro Iijima, Ho Chee Tuck, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The International Rubber Conference 2016
  • Place of Presentation: 北九州国際会議場
  • Year and Date: 2016-10-24
  • Int'l Joint Research
• [Presentation] HUGPHOS配位子を有するパラジウム錯体によるスチレンの不斉重合 (2016)
  • Author(s): Daisuke Takeuchi・Matthieu Jouffroy, Dominique Armspach, Dominique Matt, Kohtaro Osakada
  • Organizer: 第６５回高分子討論会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2016-09-14
• [Presentation] Palladium-catalyzed polycondensation utilizing chain-walking of non-conjugated dienes (2016)
  • Author(s): Liyi Tan, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: 第６５回高分子討論会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2016-09-14
• [Presentation] 二層型複核金属錯体によるオレフィン重合および共重合 (2016)
  • Author(s): 岩澤孝・竹内大介・小坂田耕太郎
  • Organizer: 第５回JACI/GSCシンポジウム
  • Place of Presentation: ANAクラウンプラザホテル神戸
  • Year and Date: 2016-06-02
• [Presentation] Polycondensation accompanying chain-walking of non-conjugated dienes by Pd catalyst (2016)
  • Author(s): Liyi Tan, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: 第６５回高分子学会年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] ジイミンパラジウム錯体によるオレフィンとアクリル酸無水物との共重合 (2016)
  • Author(s): 岩澤孝・竹内大介・小坂田耕太郎
  • Organizer: 第６５回高分子学会年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] パラジウム錯体によるイミンと一酸化炭素の共重合によるポリアミドの合成 (2016)
  • Author(s): 中丸裕一朗・竹内大介・小坂田耕太郎
  • Organizer: 第６５回高分子学会年次大会
  • Place of Presentation: 神戸国際会議場
  • Year and Date: 2016-05-25
• [Presentation] Polymerization of 3,3-dimethyl-1-butene by Diimine Pd Complexes (2015)
  • Author(s): Keisuke Ito, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: Asian Polyolefin Workshop 2015
  • Place of Presentation: 首都大学東京
  • Year and Date: 2015-11-23
  • Int'l Joint Research
• [Presentation] Stereoselective Polymerization of Chiral Olefins by Diimine Pd Complexes (2015)
  • Author(s): Yuki Tokura, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: Asian Polyolefin Workshop 2015
  • Place of Presentation: 首都大学東京
  • Year and Date: 2015-11-23
  • Int'l Joint Research
• [Presentation] Polymerization of 3,3-dimethyl-1-butene by Diimine Pd Complexes (2015)
  • Author(s): Keisuke Ito, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The 8th International Forum on Chemistry of Functional Organic Chemicals
  • Place of Presentation: 東京大学
  • Year and Date: 2015-11-15
  • Int'l Joint Research
• [Presentation] Isomerization Polymerization of Alkenylcycloalkanes by Diimine Pd Complexes (2015)
  • Author(s): Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The 11th International Conference on Advanced Polymers via Macromolecular Engineering
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2015-10-18
  • Int'l Joint Research
• [Presentation] Polymerization of 3,3-dimethyl-1-butene by Diimine Pd Complexes (2015)
  • Author(s): Keisuke Ito, Daisuke Takeuchi, Kohtaro Osakada
  • Organizer: The 11th International Conference on Advanced Polymers via Macromolecular Engineering
  • Place of Presentation: パシフィコ横浜
  • Year and Date: 2015-10-18
  • Int'l Joint Research
• [Presentation] パラジウム触媒を用いた異性化重合による官能基配列の精密に制御されたポリオレフィンの合成 (2015)
  • Author(s): 竹内大介、渡邉恵介、元国献也、小坂田耕太郎
  • Organizer: 第６４回高分子討論会
  • Place of Presentation: 東北大学
  • Year and Date: 2015-09-15
• [Presentation] ジイミンパラジウム錯体による４級炭素をもつオレフィン類の重合 (2015)
  • Author(s): 伊藤敬佑、竹内大介、小坂田耕太郎
  • Organizer: 第６４回高分子討論会
  • Place of Presentation: 東北大学
  • Year and Date: 2015-09-15
• [Presentation] パラジウム触媒による異性化重合を活用した新構造高分子の創製 (2015)
  • Author(s): 竹内大介
  • Organizer: 平成２７年度繊維学会年次大会
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2015-06-10
  • Invited
• [Presentation] トリスピラゾリルメタン配位子を有する鉄錯体によるブタジエンの重合 (2015)
  • Author(s): Ho Chee Tuck、竹内大介、小坂田耕太郎
  • Organizer: 第６４回高分子学会年次大会
  • Place of Presentation: 札幌コンベンションセンター
  • Year and Date: 2015-05-27
• [Presentation] Olefin Polymerization by Dinuclear Complexes with Double-Decker Framework (2014)
  • Author(s): 竹内大介
  • Organizer: The 9th International Conference on Cutting-Edge Organic Chemistry in Asia, The 5th New Phase International Conference on Cutting-Edge Organic Chemistry in Asia
  • Place of Presentation: ペタリンジャヤ（マレーシア）
  • Year and Date: 2014-12-01 – 2014-12-04
• [Presentation] 新しいポリオレフィンの精密合成－モノマー・触媒デザインによるアプローチ－ (2014)
  • Author(s): 竹内大介
  • Organizer: 第２９回中国四国地区高分子若手研究会
  • Place of Presentation: 高松
  • Year and Date: 2014-10-30 – 2014-10-31
  • Invited
• [Presentation] 多環状ポリオレフィンの合成と物性 (2014)
  • Author(s): 中村華綸・竹内大介・小坂田耕太郎
  • Organizer: 第６４回高分子討論会
  • Place of Presentation: 長崎
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] 新しいポリオレフィンの創製を目指したモノマー・触媒のデザイン (2014)
  • Author(s): 竹内大介
  • Organizer: 産業技術総合研究所触媒化学融合研究センター第１２回講演会
  • Place of Presentation: つくば
  • Year and Date: 2014-09-05
  • Invited
• [Presentation] Ethylene Polymerization and Copolymerization with Functional Co-Monomers by Dinculear Ni Complexes with Double-Decker Framework (2014)
  • Author(s): 竹内大介・千葉友莉子・高野重永・小坂田耕太郎
  • Organizer: XXVI International Conference on Organometallic Chemistry
  • Place of Presentation: 札幌
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] Synthesis of New Polyolefin Materials. Design of Olefin Monomers and Catalysts (2014)
  • Author(s): 竹内大介
  • Organizer: NIMS Conference
  • Place of Presentation: つくば
  • Year and Date: 2014-07-01 – 2014-07-03
  • Invited
• [Presentation] ジイミンパラジウム錯体によるメチル置換メチレンシクロヘキサンと一酸化炭素とのリビング交互共重合 (2014)
  • Author(s): 渡邉恵介・竹内大介・小坂田耕太郎
  • Organizer: 第６３回高分子学会年次大会
  • Place of Presentation: 名古屋
  • Year and Date: 2014-05-28 – 2014-05-30