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Development of novel cycloaddition reactions of 2-azaallyl radical cations with multiple bonded compounds

Research Project

Project/Area Number 18K05111
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionKitasato University

Principal Investigator

Itoh Kennosuke  北里大学, 薬学部, 准教授 (40467874)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2018: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords光付加環化反応 / ベンゾフェノン / イリジウム錯体 / 光誘起電子移動 / プロトン移動 / α-アミノアルキルラジカル / 2-アザアリルラジカルカチオン / 含窒素複素環式化合物 / 光増感 / 光付加環化 / 電子移動 / α-アミノアルキルラジカル / ニトロン / α,β-不飽和イミド / イミン / エネルギー移動 / ラジカル / ジアミノメタン / 多重結合性分子 / 付加環化反応
Outline of Final Research Achievements

This research project has been successfully provided the following achievements: (1) the development of a formal [3+3] photo-cycloaddition reactions of nitrones with N,N,N',N’-tetraalkyldiaminomethanes by using benzophenone derivatives as a photo-sensitizer, (2) the development of a formal [3+2] photo-cycloaddition reactions of imines with the diaminomethanes by using Ir(III) complex photo-sensitizers, (3) the development of a formal [3+2] photo-cycloadditions of α,β-unsaturated imide with the diaminomethanes by using by using the Ir(III) complexes, (4) the development of a formal [4+2] photo-cycloaddition reactions of α,β-unsaturated imide with N,N-dialkylanilines by using the Ir(III) complexes, (5) the elucidation of photophysical properties of the Ir(III) complexes, (6) the mechanistic study for photo-cycloaddition reactions by using computational methods. However, a reaction intermediate has been detected instead of fail to detect 2-azaally radical cation.

Academic Significance and Societal Importance of the Research Achievements

光照射下における2-アザアリルラジカルカチオンもしくは 2-アザアリルラジカルカチオン等価体特有の反応は、新規含窒素飽和複素環骨格を一挙に構築できる。したがって本反応は、新規含窒素飽和複素環を必要とする創薬化学の分野に応用され、新薬創出の一助となる可能性がある。また2-アザアリルラジカルカチオンは、π結合を有するラジカルカチオン種の中でもその構造的特徴と物理化学的性質は未知であるに等しい。したがって、この化学種を分光化学的により捕捉し構造解析を成功させ、さらにその生成機構と物理化学的性質を明らかにすることができれば、有機合成化学の基礎を拡充させることができる。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (35 results)

All 2021 2020 2019 2018

All Journal Article (11 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 10 results,  Open Access: 1 results) Presentation (23 results) (of which Int'l Joint Research: 3 results,  Invited: 1 results) Funded Workshop (1 results)

  • [Journal Article] Visible-Light-Induced Synthesis of 1,2,3,4-Tetrahydroquinolines via Formal [4+2] Cycloaddition of Acyclic α,β-Unsaturated Amides and Imides with N,N-Dialkylanilines2021

    • Author(s)
      Kennosuke Itoh, Shun-ichi Nagao, Ken Tokunaga, Shigeto Hirayama, Fumika Karaki, Takaaki Mizuguchi, Kenichiro Nagai, Noriko Sato, Mitsuaki Suzuki, Masashi Hashimoto, Hideaki Fujii
    • Journal Title

      Chem. Eur. J.

      Volume: 27 Issue: 16 Pages: 5171-5179

    • DOI

      10.1002/chem.202004186

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 1,2,5-Oxadiazinane Derivatives by Photochemical Cycloaddition of Nitrones with Diaminomethanes2020

    • Author(s)
      Itoh K, Takashino A, Ohtsuka A, Kobe M, Sawamura S, Kato R, Hirayama S, Karaki F, Mizuguchi T, Sato N, Tokunaga K, Toda Y, Suga H, Ishida H, Fujii H
    • Journal Title

      ChemPhotoChem

      Volume: Early view Issue: 6 Pages: 388-392

    • DOI

      10.1002/cptc.202000004

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Novel asymmetric photodimerization reaction of coumarin derivatives bearing a chiral 2- oxazolidinone auxiliary2019

    • Author(s)
      Itoh K, Odate F, Karikomi T, Obe K, Miyamori T, Kamiya H, Yoza K, Nagai K, Fujii H, Suga H, Tokunaga K
    • Journal Title

      RSC Adv.

      Volume: 9 Issue: 22 Pages: 12365-12369

    • DOI

      10.1039/c9ra00822e

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ligand-Dependent Site-Selective Suzuki Cross-Coupling of 4-Bromopyrazol-5-yl Triflates2019

    • Author(s)
      Sakakibara R, Itoh K, Fujii, H
    • Journal Title

      J. Org. Chem

      Volume: 84 Issue: 18 Pages: 11474-11481

    • DOI

      10.1021/acs.joc.9b01306

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Discovery of δ Opioid Receptor Full Inverse Agonists and Their Effects on Restraint Stress-induced Cognitive Impairment in Mice2019

    • Author(s)
      Hirayama S, Iwai T, Higashi E, Nakamura M, Iwamatsu C, Itoh K, Nemoto T, Tanabe M, Fujii H
    • Journal Title

      ACS Chem Neurosci

      Volume: 10 Issue: 5 Pages: 2237-2242

    • DOI

      10.1021/acschemneuro.9b00067

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] The Practical Synthesis of Dissymmetrical 1,3,5-Trioxazatriquinane Derivatives Comprised of Three Distinct Carbonyl Compounds2019

    • Author(s)
      Hirayama S, Obayashi K, Wada N, Ohyama K, Fuku S, Koyano K, Karaki F, Itoh K, Nagase H, Fujii H
    • Journal Title

      Heterocycles

      Volume: 99 Issue: 2 Pages: 1003-1019

    • DOI

      10.3987/com-18-s(f)65

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective synthesis of 8-azabicyclo[3.2.1]octanes via asymmetric 1,3-dipolar cycloadditions of cyclic azomethine ylides using a dual catalytic system2019

    • Author(s)
      Hiroyuki Suga, Masahiro Yoshiwara, Takaaki Yamaguchi, Takashi Bando, Mizuki Taguchi, Ayano Inaba, Yuichi Goto, Ayaka Kikuchi, Kennosuke Itoh, Yasunori Toda
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 11 Pages: 1552-1555

    • DOI

      10.1039/c8cc09224a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Dibenzofuran-4,6-bis(oxazoline) (DBFOX). A novel trans-chelating bis(oxazoline) ligand for asymmetric reactions2018

    • Author(s)
      Itoh, K.; Sibi, M. P.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 16 Issue: 31 Pages: 5551-5565

    • DOI

      10.1039/c8ob01010b

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Lewis Acid Catalysis in Intermolecular [2+2] Photocycloaddition of Coumarin-3-carboxamide Bearing 2-Oxazolidinone Auxiliary with n-Propyl Vinyl Ether and Vinyl Pivalate2018

    • Author(s)
      Itoh, K.; Matsuura, J.; Kamiya, H.; Kudo, R.; Takahashi, Y.; Hashimoto, Y.; Yoza, K.; Tokunaga, K.; Fujii, H.; Suga, H.
    • Journal Title

      Heterocycles

      Volume: 97 Issue: 1 Pages: 591-591

    • DOI

      10.3987/com-18-s(t)44

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Three-Component Reactions of Diazoesters, Aldehydes, and Imines Using a Dual Catalytic System Consisting of a Rhodium(II) Complex and a Lewis Acid2018

    • Author(s)
      Yasunori Toda, Wakatake Kaku, Makoto Tsuruoka, Sho Shinogaki, Tomoka Abe, Hideaki Kamiya, Ayaka Kikuchi, Kennosuke Itoh, Hiroyuki Suga
    • Journal Title

      Org. Lett.

      Volume: 20 Issue: 9 Pages: 2659-2662

    • DOI

      10.1021/acs.orglett.8b00865

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] A deprotection procedure using SO3H silica gel to remove non-silyl protecting groups2018

    • Author(s)
      Karaki F.; Kuwada M.; Tajiri S.; Kanda M.; Yanai M.; Kamimura M.; Itoh K.; Fujii H.
    • Journal Title

      Synth. Commun.

      Volume: 49 Issue: 2 Pages: 212-220

    • DOI

      10.1080/00397911.2018.1548023

    • Related Report
      2018 Research-status Report
  • [Presentation] イリジウム錯体光増感剤,チオウレア,アゾ化合物の 協働作用が可能とするテトラヒドロキノリン誘導体合成2021

    • Author(s)
      伊藤謙之介, 長尾駿一, 徳永 健・水口貴章, 唐木文霞, 平山重人, 鈴木光明, 橋本雅司, 藤井秀明
    • Organizer
      日本化学会 第 101 春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 可視光により誘起される鎖状 α,β-不飽和カルボニル化合物と N,N-ジアルキルアニリンの形式的 [4+2] 付加環化反応による テトラヒドロキノリン合成2020

    • Author(s)
      伊藤謙之介, 長尾駿一, 徳永 健, 水口貴章, 唐木文霞, 平山重人, 鈴木光明, 橋本雅司, 藤井秀明
    • Organizer
      第 49 回複素環化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 可視光を用いるドミノラジカル共役付加ー環化反応によるテトラヒドロキノリン誘導体の合成2020

    • Author(s)
      長尾 駿一,伊藤謙之介,徳永 健,水口貴章,唐木文霞,平山重人,橋本雅司,藤井秀明
    • Organizer
      日本化学会第 100 春季年会 2020 東京
    • Related Report
      2019 Research-status Report
  • [Presentation] Photo-induced formal [3+3] cycloaddition reactions of nitrones with diaminomethanes2019

    • Author(s)
      Itoh K, Takashino A, Ohtsuka A, Kobe M, Sawamura S, Kato R, Hirayama S, Karaki F, Mizuguchi T, Tokunaga K, Toda Y, Suga H, Ishida H, Fujii H
    • Organizer
      International Congress on Pure & Applied Chemistry (ICPAC) Yangon Myanmar
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 可視光応答型レトックス触媒による α-アミノアルキルラジカルの共役付加ー環化反応2019

    • Author(s)
      長尾駿一,伊藤謙之介,水口貴章,唐木文霞,平山重人,橋本雅司,徳永 健,藤井秀明
    • Organizer
      第 31 回 配位化合物の光化学討論会 富山
    • Related Report
      2019 Research-status Report
  • [Presentation] イリジウム錯体によるニトロンとシアミノメタンの可視光誘起形式的 [3+3] 付加環化反応2019

    • Author(s)
      高篠諄史,伊藤謙之介,平山重人,唐木文霞,水口貴章,石田 斉,藤井秀明
    • Organizer
      第 31 回配位化合物の光化学討論会 富山
    • Related Report
      2019 Research-status Report
  • [Presentation] 可視光応答型レドックス触媒によるα-アミノアルキルラジカルの共役付加-環化反応2019

    • Author(s)
      長尾駿一,伊藤謙之介,水口貴章,唐木文霞,平山重人,橋本雅司,徳永 健,藤井秀明
    • Organizer
      第 11 回北里化学シンポジウム 東京
    • Related Report
      2019 Research-status Report
  • [Presentation] イリジウム錯体によるニトロンとジアミノメタンの可視光誘起形式的 [3+3] 付加環化反応2019

    • Author(s)
      高篠諄史,伊藤謙之介,平山重人,唐木文霞,水口貴章,石田 斉,藤井秀明
    • Organizer
      第 11 回北里化学シンポジウム 東京
    • Related Report
      2019 Research-status Report
  • [Presentation] ニトロンとジアミノメタンの光誘起形式的 [3+3] 付加環化反応2018

    • Author(s)
      高篠諄史・○伊藤謙之介・大塚敦史・神戸瑞樹・澤村俊祐・加藤 諒・水口貴章・唐木文霞・平山重人・菅 博幸・石田 斉・藤井秀明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] テトラジンライゲーションの反応生成物をピリダジンに収束させる光酸化反応の開発2018

    • Author(s)
      ○木口卓人・唐木文霞・伊藤謙之介・藤井秀明
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Research-status Report
  • [Presentation] μ-δオピオイド受容体ヘテロダイマー選択的作用薬創出を志向したCYM51010誘導体合成2018

    • Author(s)
      ○渡邊彩花・高橋直樹・染谷僚人・松嶋あおば・石橋尚人・平山重人・宮野加奈子・伊藤謙之介・上園保仁・藤井秀明
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Research-status Report
  • [Presentation] ニトロンとジアミノメタンの光誘起形式的 [3+3] 付加環化反応2018

    • Author(s)
      〇高篠諄史・伊藤謙之介・大塚敦史・澤村俊祐・加藤諒・水口貴章・唐木文霞・平山重人・菅 博幸・石田 斉・藤井秀明
    • Organizer
      第76回有機合成化学協会関東支部シンポジウムー新潟(長岡)シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] α-ブロモケトンを用いた新規三置換オキサゾール合成法の開発と反応機構の考察2018

    • Author(s)
      〇内田遥太・柏木亜 佑・松下彩夏・石川響子・澤田英樹・沢田芳楠子・戸松美有季・長瀬 博・伊藤謙之介・ 藤井秀明
    • Organizer
      第76回有機合成化学協会関東支部シンポジウムー新潟(長岡)シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] モルヒネ非感受性μオピオイド受容体スプライスバリアント選択的作動薬を 志向したモルヒナン誘導体の合成2018

    • Author(s)
      ○本城綾香・米澤佑・御代田彩乃・平山重人・唐木文霞・伊藤謙之介・溝口広一・藤井秀明
    • Organizer
      第36回メディシナルケミストリーシンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] Development of sequential conjugate addition/cyclization reaction of carbon- centered radicals induced from tertiary amines in the presence of visible-light photoredox catalyst2018

    • Author(s)
      ○Shun-ichi Nagao, Kennosuke Itoh, Takaaki Mizuguchi, Fumika Karaki, Shigeto Hirayama, Masashi Hashimito, Hideaki Fujii
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Photo-induced formal [3+3] cycloaddition Reactions of Nitrones with Diaminomethanes2018

    • Author(s)
      Atsushi Takashino, ○Kennosuke Itoh, Atsushi Ohtsuka, Mizuki Kobe, Ryo Kato, Takaaki Mizuguchi, Fumika Karaki, Shigeto Hirayama, Hiroyuki Suga, Hitoshi Ishida, Hideaki Fujii
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] ニトロンとジアミノメタンの光誘起形式的 [3+3] 付加環化反応2018

    • Author(s)
      ○高篠諄史・伊藤謙之介・大塚敦史・澤村俊祐・加藤諒・水口貴章・唐木文霞・平山重人・菅 博幸・石田 斉・藤井秀明
    • Organizer
      第62回日本薬学会関東支部大会
    • Related Report
      2018 Research-status Report
  • [Presentation] 可視光応答型レドックス触媒による炭素ラジカル種の共役付加-環化反応2018

    • Author(s)
      ○長尾駿・伊藤謙之介・水口貴章・唐木文霞・平山重人・橋本雅司・藤井秀明
    • Organizer
      第62回日本薬学会関東支部大会
    • Related Report
      2018 Research-status Report
  • [Presentation] α-ブロモケトンを用いた新規三置換オキサゾール合成法の開発と反応機構の考察2018

    • Author(s)
      ◯内田遥太・柏木亜佑・松下彩夏・石川響子・澤田英樹・沢田芳楠子・戸松美有季・伊藤謙之介・藤井秀明
    • Organizer
      第62回日本薬学会関東支部大会
    • Related Report
      2018 Research-status Report
  • [Presentation] ニトロンとジアミノメタンの光誘起形式的[3+3]付加環化反応2018

    • Author(s)
      〇高篠諄史・伊藤謙之介・大塚敦史・加藤 諒・水口貴章・唐木文霞 ・平山 重人・菅 博幸・石田 斉・藤井秀明
    • Organizer
      2018年光化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 可視光応答型レドックス触媒による炭素ラジカル種の共役付加-環化反応2018

    • Author(s)
      〇長尾駿一・伊藤謙之介・水口貴章・唐木文霞・平山重人・橋本雅司・藤井秀明
    • Organizer
      2018年光化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] α-ブロモケトンを用いた新規三置換オキサゾール合成法の開発と反応機構の考察2018

    • Author(s)
      ○内田遥太・柏木亜佑・松下彩夏・石川響子・澤田英樹・沢田芳楠子・戸松美有季・ 伊藤謙之介・藤井秀明
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] ロジウム錯体とルイス酸の二成分触媒によるカルボニルイリドとイミンの 1.3-双極性付加環化反応2018

    • Author(s)
      ○鶴岡 信・伊藤謙之介・戸田泰徳・菅博幸
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Funded Workshop] 2019 年度第 53 回白金セミナー(北里大学薬学部)2019

    • Related Report
      2019 Research-status Report

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Published: 2018-04-23   Modified: 2022-01-27  

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