Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes
Multifunctional catalysts in organic synthesis are highly attractive, particularly in the construction of complex molecules. In this work, we report a heterogeneous bifunctional Cu-based metal–organic framework (MOF) catalyst, IMU-108, serving as both a photoredox catalyst and a cross-coupling catal...
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| مؤلفون آخرون: | , , , , , , , |
| منشور في: |
2025
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| _version_ | 1852022514048303104 |
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| author | Lu Dong (741219) |
| author2 | Hu Chen (19500) Xiaoli Tan (199417) Ning Zhang (23771) Wei Sun (93580) Dechao Li (13205977) Guangchao Liang (1741795) Yanyuan Jia (1855903) Shuo Guo (5696564) |
| author2_role | author author author author author author author author |
| author_facet | Lu Dong (741219) Hu Chen (19500) Xiaoli Tan (199417) Ning Zhang (23771) Wei Sun (93580) Dechao Li (13205977) Guangchao Liang (1741795) Yanyuan Jia (1855903) Shuo Guo (5696564) |
| author_role | author |
| dc.creator.none.fl_str_mv | Lu Dong (741219) Hu Chen (19500) Xiaoli Tan (199417) Ning Zhang (23771) Wei Sun (93580) Dechao Li (13205977) Guangchao Liang (1741795) Yanyuan Jia (1855903) Shuo Guo (5696564) |
| dc.date.none.fl_str_mv | 2025-02-24T09:44:31Z |
| dc.identifier.none.fl_str_mv | 10.1021/acscatal.5c00755.s003 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/dataset/Bifunctional_Copper_Metal_Organic_Framework_Catalyst_for_Late-Stage_Functionalization_of_Alkenes/28468893 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Medicine Microbiology Cell Biology Molecular Biology Biotechnology Chemical Sciences not elsewhere classified simple refluxing device mercaptoisophthalic acid precursors mechanistic studies suggest catalytically active sites alkenes multifunctional catalysts de novo </ possessing competent single rigid geometric structure method enables late complex molecules without 2 </ sub heterogeneous bifunctional cu maintaining catalytic activity complex molecules catalytic activity situ </ single step heterogeneous photoredox wheel motifs stage functionalization reduction ability mops ), highly attractive gram scale formed via electron transfer diaryl alkanes bromo esters boronic acids bonds result |
| dc.title.none.fl_str_mv | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| dc.type.none.fl_str_mv | Dataset info:eu-repo/semantics/publishedVersion dataset |
| description | Multifunctional catalysts in organic synthesis are highly attractive, particularly in the construction of complex molecules. In this work, we report a heterogeneous bifunctional Cu-based metal–organic framework (MOF) catalyst, IMU-108, serving as both a photoredox catalyst and a cross-coupling catalyst. IMU-108 was synthesized on a gram scale from Cu(NO<sub>3</sub>)<sub>2</sub>·3H<sub>2</sub>O and 5-mercaptoisophthalic acid precursors through a simple refluxing device. The structure of IMU-108 is formed via an <i>in situ</i> S–S bridge bond connecting zero-dimensional metal–organic polyhedra (MOPs), each composed of 12 Cu–Cu paddle-wheel motifs. These interpolyhedral S–S bonds result in a rigid geometric structure and ensure inner MOPs remain bench-stable while maintaining catalytic activity. We demonstrate the capacity of IMU-108 in heterogeneous photoredox-catalyzed cross-coupling of styrenes and α-bromo esters with boronic acids to yield various substituted 1,1-diaryl alkanes in a single step. The versatility of this method enables late-stage functionalization of complex molecules without the need for <i>de novo</i> synthesis. IMU-108 exhibits good reusability, maintaining its catalytic activity over ten consecutive reaction cycles. Furthermore, computational and mechanistic studies suggest that coordinatively unsaturated copper species on the surface of IMU-108 served as catalytically active sites, possessing competent Single-Electron Transfer (SET) reduction ability and facilitating cross-coupling reactions. |
| eu_rights_str_mv | openAccess |
| id | Manara_3e3bb9f8ae933ca7ff0ff37282ece75f |
| identifier_str_mv | 10.1021/acscatal.5c00755.s003 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/28468893 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of AlkenesLu Dong (741219)Hu Chen (19500)Xiaoli Tan (199417)Ning Zhang (23771)Wei Sun (93580)Dechao Li (13205977)Guangchao Liang (1741795)Yanyuan Jia (1855903)Shuo Guo (5696564)BiophysicsBiochemistryMedicineMicrobiologyCell BiologyMolecular BiologyBiotechnologyChemical Sciences not elsewhere classifiedsimple refluxing devicemercaptoisophthalic acid precursorsmechanistic studies suggestcatalytically active sitesalkenes multifunctional catalystsde novo </possessing competent singlerigid geometric structuremethod enables latecomplex molecules without2 </ subheterogeneous bifunctional cumaintaining catalytic activitycomplex moleculescatalytic activitysitu </single stepheterogeneous photoredoxwheel motifsstage functionalizationreduction abilitymops ),highly attractivegram scaleformed viaelectron transferdiaryl alkanesbromo estersboronic acidsbonds resultMultifunctional catalysts in organic synthesis are highly attractive, particularly in the construction of complex molecules. In this work, we report a heterogeneous bifunctional Cu-based metal–organic framework (MOF) catalyst, IMU-108, serving as both a photoredox catalyst and a cross-coupling catalyst. IMU-108 was synthesized on a gram scale from Cu(NO<sub>3</sub>)<sub>2</sub>·3H<sub>2</sub>O and 5-mercaptoisophthalic acid precursors through a simple refluxing device. The structure of IMU-108 is formed via an <i>in situ</i> S–S bridge bond connecting zero-dimensional metal–organic polyhedra (MOPs), each composed of 12 Cu–Cu paddle-wheel motifs. These interpolyhedral S–S bonds result in a rigid geometric structure and ensure inner MOPs remain bench-stable while maintaining catalytic activity. We demonstrate the capacity of IMU-108 in heterogeneous photoredox-catalyzed cross-coupling of styrenes and α-bromo esters with boronic acids to yield various substituted 1,1-diaryl alkanes in a single step. The versatility of this method enables late-stage functionalization of complex molecules without the need for <i>de novo</i> synthesis. IMU-108 exhibits good reusability, maintaining its catalytic activity over ten consecutive reaction cycles. Furthermore, computational and mechanistic studies suggest that coordinatively unsaturated copper species on the surface of IMU-108 served as catalytically active sites, possessing competent Single-Electron Transfer (SET) reduction ability and facilitating cross-coupling reactions.2025-02-24T09:44:31ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/acscatal.5c00755.s003https://figshare.com/articles/dataset/Bifunctional_Copper_Metal_Organic_Framework_Catalyst_for_Late-Stage_Functionalization_of_Alkenes/28468893CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/284688932025-02-24T09:44:31Z |
| spellingShingle | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes Lu Dong (741219) Biophysics Biochemistry Medicine Microbiology Cell Biology Molecular Biology Biotechnology Chemical Sciences not elsewhere classified simple refluxing device mercaptoisophthalic acid precursors mechanistic studies suggest catalytically active sites alkenes multifunctional catalysts de novo </ possessing competent single rigid geometric structure method enables late complex molecules without 2 </ sub heterogeneous bifunctional cu maintaining catalytic activity complex molecules catalytic activity situ </ single step heterogeneous photoredox wheel motifs stage functionalization reduction ability mops ), highly attractive gram scale formed via electron transfer diaryl alkanes bromo esters boronic acids bonds result |
| status_str | publishedVersion |
| title | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| title_full | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| title_fullStr | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| title_full_unstemmed | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| title_short | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| title_sort | Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes |
| topic | Biophysics Biochemistry Medicine Microbiology Cell Biology Molecular Biology Biotechnology Chemical Sciences not elsewhere classified simple refluxing device mercaptoisophthalic acid precursors mechanistic studies suggest catalytically active sites alkenes multifunctional catalysts de novo </ possessing competent single rigid geometric structure method enables late complex molecules without 2 </ sub heterogeneous bifunctional cu maintaining catalytic activity complex molecules catalytic activity situ </ single step heterogeneous photoredox wheel motifs stage functionalization reduction ability mops ), highly attractive gram scale formed via electron transfer diaryl alkanes bromo esters boronic acids bonds result |