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Asymmetric Borylation of Remote C(sp3)-H Bonds for the Construction of Compounds with Three-Dimensional Structural Diversity

Research Project

Project/Area Number 20K15269
Research Category

Grant-in-Aid for Early-Career Scientists

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

Principal Investigator

REYES RONALD・LAZO  北海道大学, 化学反応創成研究拠点, 特任助教 (30845475)

Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Discontinued (Fiscal Year 2022)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2023: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2022: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2021: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2020: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsborylation / asymmetric synthesis / organometallic catalysis / organic synthesis / C-H activation / C-H functionalization / remote C-H bonds / noncovalent interactions
Outline of Research at the Start

In this work, combined theoretical calculations (AFIR, DFT, etc.) and experimental methodologies will be utilized for the construction of efficient catalytic system that will enable the competent functionalization of remote C-H bonds from simple and readily available feedstocks.

Outline of Annual Research Achievements

With our interest in the development of novel methodologies for the transformation of C-H bonds in readily available feedstock chemicals, we previously demonstrated the competent activation and subsequent asymmetric borylation of g-C(sp3)-H bonds under Ir catalysis. Our collaboration with ICReDD scientists has given us infinite opportunity to further extend the reactivity of our catalytic system. Thus, guided by calculation derived transition-state models, we recently succeeded in the asymmetric borylation of more distal C-H bonds in the aliphatic hydrocarbon chain of common and readily available chemical feedstocks including biomass resources allowing for a more sustainable and efficient organic synthesis. Thereby, the borylation of e-C-H bonds, located five carbons away from the carbonyl group of the substrate, has been achieved - a direct functionalization realized using a modularly designed supramolecular catalytic assembly.

Report

(3 results)
  • 2022 Annual Research Report
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (14 results)

All 2021 2020

All Journal Article (5 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (7 results) (of which Int'l Joint Research: 4 results,  Invited: 2 results) Book (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] An Introductory Overview of C-H Bond Activation/ Functionalization Chemistry with Focus on Catalytic C(sp3)-H Bond Borylation2021

    • Author(s)
      Reyes, R. L. and Sawamura, M.
    • Journal Title

      Kimika

      Volume: 32 Pages: 70-109

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Asymmetric Remote C-H Borylation of Aliphatic Amides and Esters with a Modular Iridium Catalyst2020

    • Author(s)
      Reyes, R. L., Sato, M. Iwai, T., Suzuki, K., Maeda, S., and Sawamura, M.
    • Journal Title

      Science

      Volume: 369 Issue: 6506 Pages: 970-974

    • DOI

      10.1126/science.abc8320

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Asymmetric Synthesis of a-Aminoboronates via Rhodium-Catalyzed Enantioselective C(sp3)-H Borylation2020

    • Author(s)
      Reyes, R. L., Sato, M., Iwai, T., and Sawamura, M.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 1 Pages: 589-597

    • DOI

      10.1021/jacs.9b12013

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin, 4-[[(1R)-2'-[(triisopropylsilyl)oxy][1,1'-binaphthalen]-2-yl]oxy]-, (11bR)-(9CI).2020

    • Author(s)
      Reyes, R. L. and Sawamura, M.
    • Journal Title

      Encyclopedia of Reagents for Organic Synthesis

      Volume: - Pages: 1-2

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Construction of Medium-Sized Rings by Gold Catalysis2020

    • Author(s)
      Reyes, R. L., Iwai, T., and Sawamura, M.
    • Journal Title

      Chemical Reviews

      Volume: - Issue: 14 Pages: 8926-8947

    • DOI

      10.1021/acs.chemrev.0c00793

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Asymmetric Remote C-H Bond Borylation with a Modular Iridium Catalyst2021

    • Author(s)
      Reyes, R. L., Sato, M., Iwai, T., Suzuki, K., Maeda, S., and Sawamura, M.
    • Organizer
      101st Chemistry Society of Japan (CSJ) Annual Meeting
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Catalytic Enantioselective Remote C-H Borylation of Aliphatic Carboxylic Amides and Esters2021

    • Author(s)
      Reyes, R. L., Sato, M., Masuda, Y., Higashida, K., Iwai, T., Suzuki, K., Maeda, S., and Sawamura, M.
    • Organizer
      67th Organometallic Chemistry Symposium
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Desymmetrization of Cycloalkanes via Iridium-Catalyzed C(sp3)-H Borylation2021

    • Author(s)
      Reyes, R. L., Chong, S.-G., Iwai, T., and Sawamura, M.
    • Organizer
      67th Organometallic Chemistry Symposium
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Biologically-Relevant Organoboron Compounds through Asymmetric C-H Borylation2021

    • Author(s)
      Reyes, R. L., Sato, M., Chong, S.-G, Higashida, K., Iwai, T., Suzuki, K., Maeda, S., and Sawamura, M.
    • Organizer
      13th International Medicinal Chemistry Symposium
    • Related Report
      2021 Research-status Report
  • [Presentation] Modularly Designed Supramolecular Catalytic Assembly for the Strategic Enantioselective Borlyation of Remote C-H Bonds2021

    • Author(s)
      Reyes, R. L.
    • Organizer
      ICReDD/Hokkaido University Five Attached Institutes Joint Symposium (Online)
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] Asymmetric Synthesis of a-Aminoboronates via Rhodium-Catalyzed Enantioselective C(sp3)-H Borylation2020

    • Author(s)
      Reyes, R. L., Sato, Miyu, Iwai, T., and Sawamura M.
    • Organizer
      100th Chemistry Society of Japan (CSJ) Annual Meeting
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] Strategic Construction of Molecular Complexity via Asymmetric Remote C-H Borylation: Building Structural Diversity from Common Feedstock Chemicals2020

    • Author(s)
      Reyes, R. L., Sato, Miyu, Iwai, T., Suzuki, K., Maeda, S., and Sawamura, M
    • Organizer
      Joint Symposium of School of Science and WPI-ICReDD, Hokkaido University
    • Related Report
      2020 Research-status Report
    • Invited
  • [Book] Encyclopedia of Reagents for Organic Synthesis2020

    • Author(s)
      Reyes, R. L. and Sawamura, M.
    • Total Pages
      2
    • Publisher
      John Wiley & Sons, Ltd.
    • ISBN
      9780470842898
    • Related Report
      2020 Research-status Report
  • [Patent(Industrial Property Rights)] 単座配位尿素化合物を含む配位子とそれを含むホウ素化触媒2020

    • Inventor(s)
      R.L. Reyes, M. Sawamura
    • Industrial Property Rights Holder
      R.L. Reyes, M. Sawamura
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2022-12-28  

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