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      Development of a flow photochemical process for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence: in situ-generated 2-benzopyrylium as photoredox catalyst and reactive intermediate

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          Abstract

          A flow photochemical reaction system for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence was developed, which utilizes in situ-generated 2-benzopyrylium intermediates as the photoredox catalyst and electrophilic substrates. The key 2-benzopyrylium intermediates were generated in the flow reaction system through the intramolecular cyclization of ortho-carbonyl alkynylbenzene derivatives by the π-Lewis acidic metal catalyst AgNTf 2 and the subsequent proto-demetalation with trifluoroacetic acid. The 2-benzopyrylium intermediates underwent further photoreactions with benzyltrimethylsilane derivatives as the donor molecule in the flow photoreactor to provide 1 H-isochromene derivatives in higher yields in most cases than the batch reaction system.

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          Microreactors

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            Basics of Flow Microreactor Synthesis

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              Organometallic Flow Chemistry

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                Author and article information

                Contributors
                Role: Guest Editor
                Journal
                Beilstein J Org Chem
                Beilstein J Org Chem
                Beilstein Journal of Organic Chemistry
                Beilstein-Institut (Trakehner Str. 7-9, 60487 Frankfurt am Main, Germany )
                1860-5397
                2024
                13 August 2024
                : 20
                : 1973-1980
                Affiliations
                [1 ] Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan ( https://ror.org/01dq60k83)
                [2 ] Graduate School of Pharmaceutical Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan ( https://ror.org/01dq60k83)
                Author information
                https://orcid.org/0000-0002-0554-8652
                https://orcid.org/0000-0002-1793-856X
                https://orcid.org/0000-0001-9892-8832
                Article
                10.3762/bjoc.20.173
                11331546
                39161711
                863ce1f0-5cc6-4801-b1cd-fe0a31050da4
                Copyright © 2024, Terada et al.

                This is an open access article licensed under the terms of the Beilstein-Institut Open Access License Agreement ( https://www.beilstein-journals.org/bjoc/terms/terms), which is identical to the Creative Commons Attribution 4.0 International License ( https://creativecommons.org/licenses/by/4.0). The reuse of material under this license requires that the author(s), source and license are credited. Third-party material in this article could be subject to other licenses (typically indicated in the credit line), and in this case, users are required to obtain permission from the license holder to reuse the material.

                History
                : 27 March 2024
                : 30 July 2024
                Funding
                Funded by: Ministry of Education, Culture, Sports, Science and Technology, doi open-funder-registry10.13039/open_funder_registryhttp://dx.doi.org/10.13039/501100001700;
                Award ID: Grant-in-Aid for Scientific Research on Innovative Areas “Hybrid Catalysis for Enabling Molecular Synthesis on Demand” (JP17H06447)
                Award ID: Grant-in-Aid for Transformative Research Areas (A) “Green Catalysis Science for Renovating Transformation of Carbon-Based Resources” (JP23H04908)
                Funded by: Japan Society for the Promotion of Science, doi open-funder-registry10.13039/open_funder_registryhttp://dx.doi.org/10.13039/501100001691;
                Award ID: Grant-in-Aid for Young Scientists (JP19K15552)
                This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Hybrid Catalysis for Enabling Molecular Synthesis on Demand” (JP17H06447) and a Grant-in-Aid for Transformative Research Areas (A) “Green Catalysis Science for Renovating Transformation of Carbon-Based Resources” (JP23H04908) from MEXT, Japan and a Grant-in-Aid for Young Scientists (JP19K15552) from JSPS.
                Categories
                Full Research Paper
                Chemistry
                Organic Chemistry

                Organic & Biomolecular chemistry
                2-benzopyrylium,flow chemistry,isocromene,photochemical reaction,π-lewis acidic metal

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