Generation and characterization of highly active intermediates by hypervalent halogen and xenon compounds

• Project/Area Number: 16K15097
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: The University of Tokyo
• Principal Investigator: Miyamoto Kazunori 東京大学, 大学院薬学系研究科(薬学部), 講師 (40403696)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2016: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: 超原子価 / ヨウ素 / 臭素 / 二原子炭素 / キセノン / 脱離能 / ハロゲン / アルキニルカチオン / ジカチオン / 超原子価ハロゲン / オキソニウムジカチオン

Outline of Final Research Achievements

We successfully generated several super-reactive intermediates such as diatomic carbon, meta-benzene, bis(triflyl)carbene under mild reaction conditions in a flask and discovered their unique physical/chemical characters. The vastly enhanced nucleofugality of hypervalent halogen and xenon leaving groups are responsible for the generation of highly reactive intermediates.

Research Products

• [Journal Article] N-Alkynylpyridinium Salts: Highly Electrophilic Alkyne?Pyridine Conjugates as Precursors of Cationic Nitrogen-Embedded Polycyclic Aromatic Hydrocarbons (2018)
  • Author(s): Toriumi Naoyuki、Asano Norihito、Miyamoto Kazunori、Muranaka Atsuya、Uchiyama Masanobu
  • Journal Title: J. Am. Chem. Soc. Volume: 140 Issue: 11 Pages: 3858-3862
  • DOI: 10.1021/jacs.8b00356
  • Peer Reviewed
• [Journal Article] One-pot Annulation for Biaryl-fused Monocarba-closo-dodecaborate via Aromatic B-H Bond Disconnection (2018)
  • Author(s): Gaku Akimoto, Mai Otsuka, Kazunori Miyamoto, Atsuya Muranaka, Daisuke Hashizume, Ryo Takita, Masanobu Uchiyama
  • Journal Title: Chem. Asian J. Volume: 13 Issue: 8 Pages: 913-917
  • DOI: 10.1002/asia.201800053
  • Peer Reviewed
• [Journal Article] “Dumbbell”- and “Clackers”-Shaped Dimeric Derivatives of Monocarba-closo-dodecaborate (2018)
  • Author(s): Kitazawa Yu、Watanabe Mamoru、Masumoto Yui、Otsuka Mai、Miyamoto Kazunori、Muranaka Atsuya、Hashizume Daisuke、Takita Ryo、Uchiyama Masanobu
  • Journal Title: Angew. Chem. Int. Ed. Volume: 57 Issue: 6 Pages: 1501-1504
  • DOI: 10.1002/anie.201710122
  • Peer Reviewed
• [Journal Article] Mechanistic Study on Aryl-Exchange Reaction of Diaryl-λ3-iodane with Aryl Iodide (2017)
  • Author(s): Masumoto Yui、Miyamoto Kazunori、Iuchi Takuto、Ochiai Masahito、Hirano Keiichi、Saito Tatsuo、Wang Chao、Uchiyama Masanobu
  • Journal Title: J. Org. Chem. Volume: 83 Issue: 1 Pages: 289-295
  • DOI: 10.1021/acs.joc.7b02701
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Transition Metal-Free trans-Selective Alkynylboration of Alkynes (2017)
  • Author(s): Nogami Marina、Hirano Keiichi、Kanai Misae、Wang Chao、Saito Tatsuo、Miyamoto Kazunori、Muranaka Atsuya、Uchiyama Masanobu
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 36 Pages: 12358-12361
  • DOI: 10.1021/jacs.7b06212
  • Peer Reviewed
• [Journal Article] One-step Conversion of Levulinic Acid to Succinic Acid Using I2/t-BuOK System: The Iodoform Reaction Revisited (2017)
  • Author(s): Kawasumi Ryosuke、Narita Shodai、Miyamoto Kazunori、Tominaga Ken-ichi、Takita Ryo、Uchiyama Masanobu
  • Journal Title: Sci. Rep. Volume: 7 Issue: 1 Pages: 17967-17967
  • DOI: 10.1038/s41598-017-17116-4
  • Peer Reviewed / Open Access
• [Journal Article] Iodoarene-catalyzed oxidative transformations using molecular oxygen (2017)
  • Author(s): Miyamoto K.、Yamashita J.、Narita S.、Sakai Y.、Hirano K.、Saito T.、Wang C.、Ochiai M.、Uchiyama M.
  • Journal Title: Chem. Commun. Volume: 53 Issue: 70 Pages: 9781-9784
  • DOI: 10.1039/c7cc05160c
  • Peer Reviewed
• [Journal Article] Stille Coupling via C-N Bond Cleavage (2016)
  • Author(s): Dong-Yu Wang, Masatoshi Kawahata, Ze-Kun Yang, Kazunori Miyamoto, Shinsuke Komagawa, Kentaro Yamaguchi, Chao Wang and Masanobu Uchiyama
  • Journal Title: Nature. Commun. Volume: 7 Issue: 1 Pages: 12937-12945
  • DOI: 10.1038/ncomms12937
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Cross-Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C-O or C-N Bond Cleavage (2016)
  • Author(s): Ze-Kun Yang, Dong-Yu Wang, Hiroyuki Ogawa, Hiroki Minami, Takashi Ozaki, Tatsuo Saito, Kazunori Miyamoto, Chao Wang and Masanobu Uchiyama
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 44 Pages: 15693-15699
  • DOI: 10.1002/chem.201603436
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration (2016)
  • Author(s): Noriyuki Tezuka, Kohei Shimojo, Keiichi Hirano, Shinsuke Komagawa, Kengo Yoshida, Chao Wang, Kazunori Miyamoto, Tatsuo Saito, Ryo Takita, and Masanobu Uchiyama
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 29 Pages: 9166-9171
  • DOI: 10.1021/jacs.6b03855
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Mechanistic Studies on the Generation and Properties of Superelectrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)bromonium Ylides (2016)
  • 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
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 三価の超原子価ヨウ素試薬を用いた脂肪族カルボン酸の脱炭酸-臭素化反応の開発 (2018)
  • Author(s): 渡辺歩実、宮本和範、内山真伸
  • Organizer: 日本薬学会第138年会
• [Presentation] ジアリールクロラン(III)の合成、構造とその反応 (2018)
  • Author(s): 中島美涼、宮本和範、内山真伸
  • Organizer: 日本薬学会第138年会
• [Presentation] 超原子価アルキニルヨーダンを用いた二原子炭素発生法の開発とその性質の解明 (2017)
  • Author(s): 成田将大、宮本和範、金井美沙衣、内山真伸
  • Organizer: 日本薬学会第137年会
  • Place of Presentation: 東北大学川内北キャンパス(宮城県仙台市）
  • Year and Date: 2017-03-24
• [Presentation] 超原子価塩素化合物の合成、反応とその構造 (2017)
  • Author(s): 中島美涼、宮本和範、内山真伸
  • Organizer: 第７回CSJフェスタ2017
• [Presentation] 超原子価ヨウ素試薬を用いたシクロプロパンカルボン酸の脱炭酸的臭素化反応の開発 (2017)
  • Author(s): 渡辺歩実、宮本和範、内山真伸
  • Organizer: 第44回有機典型元素化学討論会
• [Presentation] C-H Amination Reaction Using Hypervalent λ3-bromanes (2017)
  • Author(s): Kazunori Miyamoto, Motomochi Saito, Shinichi Yamane, Tomomi Nakamura, Shunsuke Goda, Taiga Ota, Masahito Ochiai, Masanobu Uchiyama
  • Organizer: HALCHEM VIII
  • Int'l Joint Research / Invited
• [Presentation] 超原子価ヨウ素を触媒として用いる酸化反応の開発 (2017)
  • Author(s): 宮本和範、山下準平、成田将大、酒井裕太、落合正仁、内山真伸
  • Organizer: 第112回有機合成シンポジウム
• [Presentation] 超原子価ヨウ素化合物を活用したビラジカル活性種:C2発生反応の開発 (2017)
  • Author(s): 成田将大、宮本和範、内山真伸
  • Organizer: 第43回反応と合成の進歩シンポジウム
• [Presentation] 超原子価アルキニル-λ３－ヨーダンを用いた二原子炭素の発生法の開発およびその化学的性質の解明 (2016)
  • Author(s): 成田将大、宮本和範、金井美沙衣、内山真伸
  • Organizer: 第４３回有機典型元素化学討論会
  • Place of Presentation: 仙台市民会館（宮城県仙台市）
  • Year and Date: 2016-12-08
• [Presentation] 超原子価ジアリール-λ3-ブロマンによる低反発性求核試剤の求電子的アリール化反応 (2016)
  • Author(s): 宮本和範、川角亮介、増本優衣、山下泰生、中西和郎、林聡子、内山真伸
  • Organizer: 第４３回有機典型元素化学討論会
  • Place of Presentation: 仙台市民会館（宮城県仙台市）
  • Year and Date: 2016-12-08
• [Presentation] 超原子価ジアリールブロマンを用いたアルキルトリフラートの新規合成法：ヨードアルカンの超原子価への活性化 (2016)
  • Author(s): 川角亮介、宮本和範、増本優衣、内山真伸
  • Organizer: 第４２回反応と合成の進歩シンポジウム
  • Place of Presentation: 清水文化会館マリナート（静岡県静岡市）
  • Year and Date: 2016-11-07
• [Presentation] Mechanistic Investigation on the Generation and Properties of Super-electrophilic Singlet Carbenes from Bis(perfluoroalkanesulfonyl)halonium Ylides (2016)
  • Author(s): K. Miyamoto, S. Iwasaki, R. Doi, T. Ota, Y. Kawano, N. Tada, M. Ochiai, S. Hayashi, W. Nakanishi, M. Uchiyama
  • Organizer: 5th International Conference of Hypervalent Iodine Chemistry
  • Place of Presentation: Eurotel Victoria (Swiss)
  • Year and Date: 2016-07-03
  • Int'l Joint Research
• [Remarks] 東京大学 大学院薬学系研究科 薬学部 基礎有機化学教室
  • URL: http://www.f.u-tokyo.ac.jp/~kisoyuki/
• [Patent(Industrial Property Rights)] カルボン酸又はその塩の製造方法 (2016)
  • Inventor(s): 内山真伸、宮本和範
  • Industrial Property Rights Holder: 内山真伸、宮本和範
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-07-14