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Quantitative evaluation of relative leaving group ability of hypervalent organobromanyl groups

Research Project

Project/Area Number 25460016
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionThe University of Tokyo (2014-2015)
The University of Tokushima (2013)

Principal Investigator

Kazunori Miyamoto  東京大学, 薬学研究科(研究院), 講師 (40403696)

Project Period (FY) 2013-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2015: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2013: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Keywords超原子価 / ハロゲン / 臭素 / 塩素 / キセノン / 脱離能 / ジアゾニウム / ヨウ素 / SN1 / 反応速度
Outline of Final Research Achievements

The chemistry of hypervalent organobromine(III) and chlorine(III) compounds are still remained to be established. Therefore, we have investigated the driving force of their reactivity and its synthetic use in current organic synthesis. In this research project, we synthesized hypervalent organobromine(III) and chlorine(III) compounds suitable for kinetic study in order to evaluate the relative leaving group ability. Rate constants for unimolecular decomposition of these reagents found to be effective to compare leaving group ability of hypervalent haloganyl groups. In addition, during the above kinetic study, we found several new reactions which are useful for organic synthesis such as C-H activation of hydrocarbons with thermal decomposition of halonium ylide and aryl transfer reaction of diarylbromane(III) with iodoarenes.

Report

(4 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Research-status Report
  • 2013 Research-status Report
  • Research Products

    (35 results)

All 2016 2015 2014 2013 Other

All Journal Article (11 results) (of which Peer Reviewed: 11 results,  Acknowledgement Compliant: 6 results,  Open Access: 1 results) Presentation (19 results) (of which Int'l Joint Research: 6 results,  Invited: 1 results) Book (1 results) Remarks (4 results)

  • [Journal Article] Mechanistic Studies on the Generation and Properties of Superelectrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)bromonium Ylides2016

    • Author(s)
      Miyamoto, Kazunori; Iwasaki, Susumu; Doi, Ryusuke; Ota, Taiga; Kawano, Yufuko; Yamashita, Junpei; Sakai, Yuuta; Tada, Norihiro; Ochiai, Masahito; Hayashi, Satoko; Waro, Nakanishi; Masanobu, Uchiyama
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 81 Issue: 8 Pages: 3188-3198

    • DOI

      10.1021/acs.joc.6b00142

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Stereoselective synthesis and reaction of gold(I) (Z)-enethiolates2015

    • Author(s)
      Miyamoto, Kazunori; Hirobe, Masaya; Uchiyama, Masanobu; Ochiai, Masahito
    • Journal Title

      Chemical Communications

      Volume: 51 Issue: 37 Pages: 7962-7965

    • DOI

      10.1039/c5cc02000j

    • Related Report
      2015 Annual Research Report 2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Conjugation between σ- and π-Aromaticity in 1-C-Arylated Monocarba-closo-dodecaborate Anions2015

    • Author(s)
      Otsuka, Mai; Takita, Ryo; Kanazawa, Junichiro; Miyamoto, Kazunori; Muranaka, Atsuya; Uchiyama, Masanobu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 137 Issue: 48 Pages: 15082-15085

    • DOI

      10.1021/jacs.5b10321

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Dialkylzinc-mediated allylic polyfluoroarylation reaction2015

    • Author(s)
      Kurauchi, Daisuke; Hirano, Keiichi; Kato, Hisano; Saito, Tatsuo; Miyamoto, Kazunori; Uchiyama, Masanobu
    • Journal Title

      Tetrahedron

      Volume: 71 Issue: 35 Pages: 5849-5857

    • DOI

      10.1016/j.tet.2015.05.107

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Metal-free C-H amination of un-activated hydrocarbons with sulfonylimino-λ3-bromanes generated in situ from (diacetoxybromo)benzene2015

    • Author(s)
      Kazunori Miyamoto, Taiga Ota, Md. Mahbubul Hoque, Masahito Ochiai
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 13 Issue: 7 Pages: 2129-2133

    • DOI

      10.1039/c4ob02160f

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Unexpected Metal-Free Transformation of gem-Dibromomethylenes to Ketones under Acetylation Conditions.2015

    • Author(s)
      Kimura, R.; Sawayama, Y.; Nakazaki, A.; Miyamoto, K.; Uchiyama, M.; Nishikawa, T.
    • Journal Title

      Chem. Asian J.

      Volume: 10 Issue: 4 Pages: 1035-1041

    • DOI

      10.1002/asia.201403277

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Bromonium, [4-(Trifluoromethyl)phenyl][[(trifluoromethyl)sulfonyl]amino]-, Inner Salt2015

    • Author(s)
      Kazunori Miyamoto
    • Journal Title

      Encyclopedia of Reagent for Organic Synthesis

      Volume: なし Pages: 1-6

    • DOI

      10.1002/047084289x.rn01795

    • ISBN
      9780470842898
    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Hypervalent Organo-&lambda;<sup>3</sup>-bromanes and Their Reactions by Using Leaving Group Ability of &lambda;<sup>3</sup>-Bromanyl Group2014

    • Author(s)
      Kazunori Miyamoto
    • Journal Title

      YAKUGAKU ZASSHI

      Volume: 134 Issue: 12 Pages: 1287-1300

    • DOI

      10.1248/yakushi.14-00221

    • NAID

      130004712992

    • ISSN
      0031-6903, 1347-5231
    • Year and Date
      2014-12-01
    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Reactivity of Hydroxy- and Aquo(hydroxy)-λ3-iodane-Crown Ether Complexes2014

    • Author(s)
      Miyamoto K., Yokota Y., Suefuji T., Yamaguchi K., Ozawa M., Ochiai M.
    • Journal Title

      Chem. Eur. J.

      Volume: 20 Issue: 18 Pages: 5447-5453

    • DOI

      10.1002/chem.201304961

    • Related Report
      2014 Research-status Report 2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Guaiacol2014

    • Author(s)
      Kazunori Miyamoto
    • Journal Title

      Encyclopedia of Reagent for Organic Synthesis

      Volume: なし Pages: 1-3

    • DOI

      10.1002/047084289x.rn01705

    • ISBN
      9780470842898
    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Journal Article] In Situ Generation Technology of β-Butoxycarbonyliodonium Ylide: A Hypervalent Analogue of the Darzens Reagent2013

    • Author(s)
      Miyamoto K., Suzuki M., Suefuji T., Ochiai M.
    • Journal Title

      Eur. J. Org. Chem.

      Volume: 2013 Issue: 18 Pages: 3662-3666

    • DOI

      10.1002/ejoc.201300413

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Presentation] Mechanistic Investigation on the Generation and Properties of Super-electrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)halonium Ylides2016

    • Author(s)
      Kazunori Miyamoto, Susumu Iwasaki, Ryusuke Doi, Taiga Ota, Yufuko Kawano, Norihiro Tada, Masahito Ochiai, Satoko Hayashi, Waro Nakanishi, Masanobu Uchiyama
    • Organizer
      5th International Conference on Hypervalent Iodine Chemistry
    • Place of Presentation
      Eurotel Victoria, Les Diablerets (スイス)
    • Year and Date
      2016-07-03
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Iodoarene-catalyzed Hofmann rearrangement of primary amide2015

    • Author(s)
      Kazunori Miyamoto, Yuuta Sakai, Shunsuke Goda, Masahito Ochiai, Masanobu Uchiyama
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Hawaii convention center (アメリカ)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Hypervalent diaryl-λ3-bromane-mediated iodine/triflate exchange of iodoalkanes: Direct arylation of iodoalkanes with diaryl(triflato)-λ3-bromane2015

    • Author(s)
      Ryosuke Kawasumi, Kazunori Miyamoto, Yui Masumoto, Masanobu Uchiyama
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Hawaii convention center (アメリカ)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Mechanistic study on direct aryl transfer of diaryliodane(III) with aryl iodide2015

    • Author(s)
      Yui Masumoto, Takuto Iuchi, Masahito Ochiai, Kazunori Miyamoto, Masanobu Uchiyama
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Hawaii convention center (アメリカ)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Transition metal-free regioselective α-C-H amination of ethers at ambient temperature: Radical-induced amination using (diacetoxyiodo)benzene-sulfonamide2015

    • Author(s)
      Junpei Yamashita, Kazunori Miyamoto, Masanobu Uchiyama
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Hawaii convention center (アメリカ)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Generation and Properties of Super-electrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)bromonium Ylides2015

    • Author(s)
      Kazunori Miyamoto
    • Organizer
      東大・薬-ケンブリッジ大・CIMR/Dept.Chem.合同シンポジウム
    • Place of Presentation
      McGrath Centre, St Catherine’s College, Cambridge(イギリス)
    • Year and Date
      2015-11-23
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ビス(ペルフルオロアルキルスルホニル)カルベン:超求電子性カルベンの発 生とその反応特性2015

    • Author(s)
      宮本和範, 岩崎進, 土井龍輔, 河野由布子, 多田教浩, 落合正仁, 中西和郎, 林聡子, 内山真伸
    • Organizer
      第41回反応と合成の進歩シンポジウム
    • Place of Presentation
      近畿大学11月ホール(大阪府)
    • Year and Date
      2015-10-26
    • Related Report
      2015 Annual Research Report
  • [Presentation] CH 活性化の新しい方法: PhI(OAc)2 -スルホンアミドによるエーテルのメタルフリー α 位 CH アミノ化反応2015

    • Author(s)
      山下準平、宮本和範、内山真伸
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部 船橋キャンパス(千葉県)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Research-status Report
  • [Presentation] ヨードアレーンへのジアリールヨーダン(Ⅲ)による直接アリール基転移反応の反応機構解析2015

    • Author(s)
      増本優衣、井内拓人、落合 正仁、宮本 和範、内山 真伸
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸学院大学(兵庫県)
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] ジアリールハロガン(III) のSN1 型加溶媒分解反応を活用した三価の超原子価ハロガン置換基の脱離能の評価2014

    • Author(s)
      宮本和範、中西和郎、林聡子、落合正仁、内山真伸
    • Organizer
      第40回反応と合成の進歩シンポジウム
    • Place of Presentation
      東北大学川内萩ホール(宮城県)
    • Year and Date
      2014-11-10 – 2014-11-11
    • Related Report
      2014 Research-status Report
  • [Presentation] 末端酸化剤として酸素を利用する、アリール-λ3-ヨーダンによる触媒的Hofmann 転位反応2014

    • Author(s)
      酒井祐太、宮本和範、山下準平、内山真伸
    • Organizer
      第17回ヨウ素学会シンポジウム
    • Place of Presentation
      千葉大学けやき会館(千葉県)
    • Year and Date
      2014-09-19
    • Related Report
      2014 Research-status Report
  • [Presentation] Iodoarene-Catalyzed Oxidative Transformations Using Molecular Oxygen as Oxidant2014

    • Author(s)
      Kazunori Miyamoto, Yuuta Sakai, Junpei Yamashita, Masanobu Uchiyama
    • Organizer
      international conference on hypervalent iodine chemistry
    • Place of Presentation
      Hilton Narita(Chiba)
    • Year and Date
      2014-07-02 – 2014-07-05
    • Related Report
      2014 Research-status Report
  • [Presentation] ジアリールヨーダン(III)によるヨードアレーンのI-アリール化反応2014

    • Author(s)
      井内  拓人、山下  泰生、高丸 菜々子、落合 正仁、宮本 和範
    • Organizer
      日本薬学会第134年会
    • Place of Presentation
      熊本市総合体育館(熊本県)
    • Related Report
      2013 Research-status Report
  • [Presentation] Br-ヒドロキシベンズブロモキソロンの酸化反応2014

    • Author(s)
      辻  駿佑、齊藤 基道、落合 正仁、宮本 和範
    • Organizer
      日本薬学会第134年会
    • Place of Presentation
      熊本市総合体育館(熊本県)
    • Related Report
      2013 Research-status Report
  • [Presentation] 三価の超原子価有機臭素化合物の合成とその脱離能を推進力とする有機合成反応の開発2014

    • Author(s)
      宮本 和範
    • Organizer
      日本薬学会第134年会
    • Place of Presentation
      ホテル日航熊本(熊本県)
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] C-H Amination of unactivated alkanes with hypervalent bromane(III) and amides2013

    • Author(s)
      Kazunori Miyamoto, Taiga Ota, Masahito Ochiai
    • Organizer
      Nagoya Symposium, 2013
    • Place of Presentation
      名古屋大学(愛知県)
    • Related Report
      2013 Research-status Report
  • [Presentation] Direct aromatic C-H amination with hypervalent diacetoxybromane(III)2013

    • Author(s)
      Shunsuke Goda, Kazunori Miyamoto, Masahito Ochiai
    • Organizer
      Direct aromatic C-H amination with hypervalent diacetoxybromane(III)
    • Place of Presentation
      名古屋大学(愛知県)
    • Related Report
      2013 Research-status Report
  • [Presentation] 分子状酸素を酸化剤とするヨードアレーン触媒を用いた1,2-ジオールの酸化的開裂反応2013

    • Author(s)
      宮本 和範、山下 準平、小笠 紗也加、落合 正仁
    • Organizer
      第16回ヨウ素学会シンポジウム
    • Place of Presentation
      千葉大学(千葉県)
    • Related Report
      2013 Research-status Report
  • [Presentation] 分子状酸素を酸化剤とする、ヨードアレーン触媒を用いたHofmann 転位反応2013

    • Author(s)
      酒井 祐太、宮本 和範、落合 正仁
    • Organizer
      第52回日本薬学会中国四国支部学術大会
    • Place of Presentation
      松山大学(愛媛県)
    • Related Report
      2013 Research-status Report
  • [Book] 現代化学(超原子価で切拓く未踏ハロゲンの化学)2015

    • Author(s)
      宮本和範、落合正仁
    • Total Pages
      6
    • Publisher
      東京化学同人
    • Related Report
      2015 Annual Research Report
  • [Remarks] 東京大学大学院薬学系研究科 基礎有機化学教室

    • URL

      http://www.f.u-tokyo.ac.jp/~kisoyuki/

    • Related Report
      2015 Annual Research Report
  • [Remarks] 基礎有機化学教室

    • URL

      http://www.f.u-tokyo.ac.jp/~kisoyuki/

    • Related Report
      2014 Research-status Report
  • [Remarks] 薬品製造化学分野

    • URL

      http://www.tokushima-u.ac.jp/ph/faculty/labo/org/

    • Related Report
      2013 Research-status Report
  • [Remarks] 米科学誌「サイエンス」掲載

    • URL

      http://www.tokushima-u.ac.jp/ph/docs/2011101800145/

    • Related Report
      2013 Research-status Report

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Published: 2014-07-25   Modified: 2019-07-29  

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