Generation of radical species by the design of sulfonyl groups

• Project/Area Number: 21K05068
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Nagoya University
• Principal Investigator: Nambo Masakazu 名古屋大学, トランスフォーマティブ生命分子研究所, 特任准教授 (10705528)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2023: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2022: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2021: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: ラジカル種 / スルホニル基 / 炭素-スルホニル結合活性化 / スルホン / 分子触媒 / フォトレドックス触媒 / １電子還元 / 可視光フォトレドックス触媒 / 付加反応 / ホモカップリング / ラジカル

Outline of Research at the Start

ラジカル種は魅力的な反応性化学種でありながら発生可能な前駆体が限られることや、高度に官能基化されたラジカル種の活用が困難であることが現代の精密有機合成におけるボトルネックとなっている。そのため本研究では安定かつ調製が容易なスルホンをラジカル種前駆体として活用する新手法をを見出すことで根本的な解決を目指す。

Outline of Final Research Achievements

We developed a new method for reductive activation of alkyl sulfones to generate synthetically useful alkyl radical under mild conditions. By utilizing this method, we succeeded in applying it to radical transformations such as the Giese reaction. It was found that not only the choice of single-electron reducing agent but also the substituent on the sulfonyl group is extremely important in the generation of radical species.

Academic Significance and Societal Importance of the Research Achievements

本研究を通じ、スルホニル基の分子設計によってスルホンが有用なラジカル種前駆体として機能することを明らかにした。この知見を活用することで、新しい形式のラジカル分子変換の開拓が期待される。

Research Products

• [Int'l Joint Research] クイーンズ大学(カナダ)
• [Int'l Joint Research] クイーンズ大学(カナダ)
• [Int'l Joint Research] クイーンズ大学(カナダ)
• [Journal Article] Lecture Tour upon Receiving the 18^th and 19^th Lectureship Award MBLA (2024)
  • Author(s): Nambo Masakazu、Yamatsugu Kenzo
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 82 Issue: 4 Pages: 382-394
  • DOI: 10.5059/yukigoseikyokaishi.82.382
  • ISSN: 0037-9980, 1883-6526
  • Year and Date: 2024-04-01
• [Journal Article] Visible-light photoredox-catalyzed coupling of alkylsulfones with α-(trifluoromethyl)styrenes (2023)
  • Author(s): Tahara Yasuyo、Ghosh Koushik、Nambo Masakazu
  • Journal Title: Canadian Journal of Chemistry Volume: 101 Issue: 7 Pages: 491-496
  • DOI: 10.1139/cjc-2022-0271
  • Peer Reviewed
• [Journal Article] Sequential Transformations of Organosulfones on the Basis of Properties of Sulfonyl Groups (2022)
  • Author(s): Nambo Masakazu、Crudden Cathleen M.
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 80 Issue: 3 Pages: 222-231
  • DOI: 10.5059/yukigoseikyokaishi.80.222
  • ISSN: 0037-9980, 1883-6526
  • Year and Date: 2022-03-01
  • Int'l Joint Research
• [Journal Article] Photocatalytic Desulfonylative Homocoupling of Benzylic Sulfone Derivatives (2022)
  • Author(s): Nambo Masakazu、Crudden Cathleen M.、Ohkura Ryusei、Ohtsuka Motoo、Yim Jacky C.-H.
  • Journal Title: Synlett Volume: 34 Issue: 01 Pages: 81-85
  • DOI: 10.1055/a-1942-5695
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Desulfonylative Coupling of Alkylsulfones with <i>gem-</i>Difluoroalkenes by Visible-Light Photoredox Catalysis (2022)
  • Author(s): Nambo Masakazu、Ghosh Koushik、Yim Jacky C.-H.、Tahara Yasuyo、Inai Naoto、Yanai Takeshi、Crudden Cathleen M.
  • Journal Title: ACS Catalysis Volume: 12 Issue: 15 Pages: 9526-9532
  • DOI: 10.1021/acscatal.2c02233
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Desulfonylative Transformations of Sulfones by Transition-Metal Catalysis, Photocatalysis, and Organocatalysis (2022)
  • Author(s): Nambo Masakazu、Maekawa Yuuki、Crudden Cathleen M.
  • Journal Title: ACS Catalysis Volume: 12 Issue: 5 Pages: 3013-3032
  • DOI: 10.1021/acscatal.1c05608
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis and Characterization of Enantiopure Chiral Bis NHC-Stabilized Edge-Shared Au₁₀ Nanocluster with Unique Prolate Shape (2022)
  • Author(s): Man Renee W. Y.、Yi Hong、Malola Sami、Takano Shinjiro、Tsukuda Tatsuya、H?kkinen Hannu、Nambo Masakazu、Crudden Cathleen M.
  • Journal Title: Journal of the American Chemical Society Volume: 144 Issue: 5 Pages: 2056-2061
  • DOI: 10.1021/jacs.1c11857
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] NHC-Stabilized Au10 Nanoclusters and Their Conversion to Au25 Nanoclusters (2022)
  • Author(s): Lummis Paul A.、Osten Kimberly M.、Levchenko Tetyana I.、Sabooni Asre Hazer Maryam、Malola Sami、Owens-Baird Bryan、Veinot Alex J.、Albright Emily L.、Schatte Gabriele、Takano Shinjiro、Kovnir Kirill、Stamplecoskie Kevin G.、Tsukuda Tatsuya、H?kkinen Hannu、Nambo Masakazu、Crudden Cathleen M.
  • Journal Title: JACS Au Volume: 2 Issue: 4 Pages: 875-885
  • DOI: 10.1021/jacsau.2c00004
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Synthesis of quaternary centres by single electron reduction and alkylation of alkylsulfones (2021)
  • Author(s): Nambo Masakazu、Tahara Yasuyo、Yim Jacky C.-H.、Yokogawa Daisuke、Crudden Cathleen M.
  • Journal Title: Chemical Science Volume: 12 Issue: 13 Pages: 4866-4871
  • DOI: 10.1039/d1sc00133g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Transition Metal‐Catalyzed Cross‐Couplings of Benzylic Sulfone Derivatives (2021)
  • Author(s): Nambo Masakazu、Crudden Cathleen M.
  • Journal Title: The Chemical Record Volume: 21 Issue: 12 Pages: 3978-3989
  • DOI: 10.1002/tcr.202100210
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis and enantioseparation of chiral Au₁₃ nanoclusters protected by bis-<i>N</i>-heterocyclic carbene ligands (2021)
  • Author(s): Yi Hong、Osten Kimberly M.、Levchenko Tetyana I.、Veinot Alex J.、Aramaki Yoshitaka、Ooi Takashi、Nambo Masakazu、Crudden Cathleen M.
  • Journal Title: Chemical Science Volume: 12 Issue: 31 Pages: 10436-10440
  • DOI: 10.1039/d1sc03076k
  • Peer Reviewed / Int'l Joint Research
• [Presentation] フッ素官能基を活かしたスルホン化合物の新しい分子変換 (2024)
  • Author(s): 南保正和
  • Organizer: 第19回フッ素相模セミナー
  • Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: 第14回大津会議
  • Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Ludwig Maximilian University of Munich
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Max-Planck Institute for Coal Research
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, ETH Zurich
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Princeton University
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Merck
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Massachusetts Institute of Technology
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Harvard University
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, The California Institute of Technology
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, University of California, Berkeley
  • Int'l Joint Research / Invited
• [Presentation] New Transformations of Organosulfones through Carbon-Sulfonyl Bond Activation (2024)
  • Author(s): Masakazu Nambo
  • Organizer: Merck-Banyu Lecture, Stanford University
  • Int'l Joint Research / Invited
• [Presentation] Radical-based Transformations through Reductive Activation of Carbon-Sulfonyl Bonds (2024)
  • Author(s): Masakazu Nambo
  • Organizer: 第104春季年会, MBLA20周年記念特別講演会
  • Invited
• [Presentation] スルホニル基を活かした逐次的分子変換反応の開発 (2022)
  • Author(s): 南保 正和
  • Organizer: 第34回万有札幌シンポジウム
  • Invited
• [Presentation] Synthesis of Quaternary Centres through Single Electron Reduction of Alkylsulfones (2022)
  • Author(s): Masakazu Nambo, Koushik Ghosh, Jacky C.-H. Yim, Yasuyo Tahara, Cathleen M. Crudden
  • Organizer: International Congress on Pure & Applied Chemistry (ICPAC Kota Kinabalu 2022)
  • Int'l Joint Research / Invited
• [Presentation] 可視光フォトレドックス触媒によるアルキルスルホンとgem-ジフルオロアルケンのカップリング反応 (2022)
  • Author(s): Masakazu Nambo, Koushik Ghosh, Jacky C.-H. Yim, Yasuyo Tahara, Cathleen M. Crudden
  • Organizer: 第102春季年会
• [Presentation] スルホニル基の特性を活かした新規分子構築法の開発 (2021)
  • Author(s): 南保正和
  • Organizer: 第37回有機合成化学セミナー
  • Invited
• [Book] 有機化学イノベーション (2024)
  • Author(s): 南保正和 (山本尚監修)
  • Total Pages: 12
  • Publisher: 東京化学同人
• [Patent(Industrial Property Rights)] アルキル置換多環芳香族化合物の製造方法 (2024)
  • Inventor(s): 南保正和、他3名
  • Industrial Property Rights Holder: 南保正和、他3名
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2024-012055
  • Filing Date: 2024
  • Acquisition Date: 2024