The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles
Abstract Friedel-Crafts Arylation (the Scholl reaction) is the coupling of two aromatic rings with the aid of a strong Lewis or Brønsted acid. This historically significant C–C bond forming reaction normally leads to aromatic products, often as oligomeric mixtures, dictated by the large stabilizatio...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38945-0 |
| _version_ | 1797811422322753536 |
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| author | Justin T. Weatherford-Pratt Jacob A. Smith Jeremy M. Bloch Megan N. Ericson Jeffery T. Myers Karl S. Westendorff Diane A. Dickie W. Dean Harman |
| author_facet | Justin T. Weatherford-Pratt Jacob A. Smith Jeremy M. Bloch Megan N. Ericson Jeffery T. Myers Karl S. Westendorff Diane A. Dickie W. Dean Harman |
| author_sort | Justin T. Weatherford-Pratt |
| collection | DOAJ |
| description | Abstract Friedel-Crafts Arylation (the Scholl reaction) is the coupling of two aromatic rings with the aid of a strong Lewis or Brønsted acid. This historically significant C–C bond forming reaction normally leads to aromatic products, often as oligomeric mixtures, dictated by the large stabilization gained upon their rearomatization. The coordination of benzene by a tungsten complex disrupts the natural course of this reaction sequence, allowing for Friedel-Crafts Arylation without rearomatization or oligomerization. Subsequent addition of a nucleophile to the coupled intermediate leads to functionalized cyclohexenes. In this work, we show that by coordinating benzene to tungsten through two carbons (dihapto-coordinate), a rarely observed double protonation of the bound benzene is enabled, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst. |
| first_indexed | 2024-03-13T07:22:27Z |
| format | Article |
| id | doaj.art-99653cf38f1b4ce6a6be838265b235d6 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-13T07:22:27Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-99653cf38f1b4ce6a6be838265b235d62023-06-04T11:33:40ZengNature PortfolioNature Communications2041-17232023-05-011411810.1038/s41467-023-38945-0The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophilesJustin T. Weatherford-Pratt0Jacob A. Smith1Jeremy M. Bloch2Megan N. Ericson3Jeffery T. Myers4Karl S. Westendorff5Diane A. Dickie6W. Dean Harman7Department of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaDepartment of Chemistry, University of VirginiaAbstract Friedel-Crafts Arylation (the Scholl reaction) is the coupling of two aromatic rings with the aid of a strong Lewis or Brønsted acid. This historically significant C–C bond forming reaction normally leads to aromatic products, often as oligomeric mixtures, dictated by the large stabilization gained upon their rearomatization. The coordination of benzene by a tungsten complex disrupts the natural course of this reaction sequence, allowing for Friedel-Crafts Arylation without rearomatization or oligomerization. Subsequent addition of a nucleophile to the coupled intermediate leads to functionalized cyclohexenes. In this work, we show that by coordinating benzene to tungsten through two carbons (dihapto-coordinate), a rarely observed double protonation of the bound benzene is enabled, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.https://doi.org/10.1038/s41467-023-38945-0 |
| spellingShingle | Justin T. Weatherford-Pratt Jacob A. Smith Jeremy M. Bloch Megan N. Ericson Jeffery T. Myers Karl S. Westendorff Diane A. Dickie W. Dean Harman The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles Nature Communications |
| title | The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles |
| title_full | The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles |
| title_fullStr | The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles |
| title_full_unstemmed | The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles |
| title_short | The double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles |
| title_sort | double protonation of dihapto coordinated benzene complexes enables dearomatization using aromatic nucleophiles |
| url | https://doi.org/10.1038/s41467-023-38945-0 |
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