Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study
Photoredox catalysis has emerged as an alternative to classical cross-coupling reactions, promoting new reactivities. Recently, the use of widely abundant alcohols and aryl bromides as coupling reagents was demonstrated to promote efficient coupling through the Ir/Ni dual photoredox catalytic cycle....
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-05-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/11/9145 |
| _version_ | 1797597456349790208 |
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| author | Nil Sanosa Pedro Ruiz-Campos Diego Ambrosi Diego Sampedro Ignacio Funes-Ardoiz |
| author_facet | Nil Sanosa Pedro Ruiz-Campos Diego Ambrosi Diego Sampedro Ignacio Funes-Ardoiz |
| author_sort | Nil Sanosa |
| collection | DOAJ |
| description | Photoredox catalysis has emerged as an alternative to classical cross-coupling reactions, promoting new reactivities. Recently, the use of widely abundant alcohols and aryl bromides as coupling reagents was demonstrated to promote efficient coupling through the Ir/Ni dual photoredox catalytic cycle. However, the mechanism underlying this transformation is still unexplored, and here we report a comprehensive computational study of the catalytic cycle. We have shown that nickel catalysts can promote this reactivity very efficiently through DFT calculations. Two different mechanistic scenarios were explored, suggesting that two catalytic cycles operate simultaneously depending on the concentration of the alkyl radical. |
| first_indexed | 2024-03-11T03:06:19Z |
| format | Article |
| id | doaj.art-1df6b1c686e143b58601f8d614f1b198 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T03:06:19Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-1df6b1c686e143b58601f8d614f1b1982023-11-18T07:55:01ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-05-012411914510.3390/ijms24119145Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational StudyNil Sanosa0Pedro Ruiz-Campos1Diego Ambrosi2Diego Sampedro3Ignacio Funes-Ardoiz4Centro de Investigación en Síntesis Química (CISQ), Department of Chemistry, Universidad de la Rioja, Madre de Dios 53, 26004 Logroño, SpainCentro de Investigación en Síntesis Química (CISQ), Department of Chemistry, Universidad de la Rioja, Madre de Dios 53, 26004 Logroño, SpainCentro de Investigación en Síntesis Química (CISQ), Department of Chemistry, Universidad de la Rioja, Madre de Dios 53, 26004 Logroño, SpainCentro de Investigación en Síntesis Química (CISQ), Department of Chemistry, Universidad de la Rioja, Madre de Dios 53, 26004 Logroño, SpainCentro de Investigación en Síntesis Química (CISQ), Department of Chemistry, Universidad de la Rioja, Madre de Dios 53, 26004 Logroño, SpainPhotoredox catalysis has emerged as an alternative to classical cross-coupling reactions, promoting new reactivities. Recently, the use of widely abundant alcohols and aryl bromides as coupling reagents was demonstrated to promote efficient coupling through the Ir/Ni dual photoredox catalytic cycle. However, the mechanism underlying this transformation is still unexplored, and here we report a comprehensive computational study of the catalytic cycle. We have shown that nickel catalysts can promote this reactivity very efficiently through DFT calculations. Two different mechanistic scenarios were explored, suggesting that two catalytic cycles operate simultaneously depending on the concentration of the alkyl radical.https://www.mdpi.com/1422-0067/24/11/9145cross-couplingdensity functional theorynickel catalysisradicalsreaction mechanisms |
| spellingShingle | Nil Sanosa Pedro Ruiz-Campos Diego Ambrosi Diego Sampedro Ignacio Funes-Ardoiz Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study International Journal of Molecular Sciences cross-coupling density functional theory nickel catalysis radicals reaction mechanisms |
| title | Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study |
| title_full | Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study |
| title_fullStr | Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study |
| title_full_unstemmed | Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study |
| title_short | Investigating the Mechanism of Ni-Catalyzed Coupling of Photoredox-Generated Alkyl Radicals and Aryl Bromides: A Computational Study |
| title_sort | investigating the mechanism of ni catalyzed coupling of photoredox generated alkyl radicals and aryl bromides a computational study |
| topic | cross-coupling density functional theory nickel catalysis radicals reaction mechanisms |
| url | https://www.mdpi.com/1422-0067/24/11/9145 |
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