Room‐Temperature Copper‐Catalyzed Etherification of Aryl Bromides

We disclose the development of a Cu‐catalyzed C−O coupling method utilizing a new N1,N2‐diarylbenzene‐1,2‐diamine ligand, L8. Under optimized reaction conditions, structurally diverse aryl and heteroaryl bromides underwent efficient coupling with a variety of alcohols at room temperature using an L8...

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Bibliographic Details
Published in:Angewandte Chemie 2024-05, Vol.136 (19), p.n/a
Main Authors: Strauss, Michael J., Greaves, Megan E., Kim, Seoung‐Tae, Teijaro, Christiana N., Schmidt, Michael A., Scola, Paul M., Buchwald, Stephen L.
Format: Article
Language:English
Subjects:
Alcohols
Aromatic compounds
Bonding
Bromides
Catalysts
Chemical reactions
Copper
Coupling
Coupling methods
Cu Catalysis
C−O Coupling
Diamines
Functional groups
Ligand Design
Ligands
Room temperature
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Summary:We disclose the development of a Cu‐catalyzed C−O coupling method utilizing a new N1,N2‐diarylbenzene‐1,2‐diamine ligand, L8. Under optimized reaction conditions, structurally diverse aryl and heteroaryl bromides underwent efficient coupling with a variety of alcohols at room temperature using an L8‐based catalyst. Notably, the L8‐derived catalyst exhibited enhanced activity when compared to the L4‐based system previously disclosed for C−N coupling, namely the ability to functionalize aryl bromides containing acidic functional groups. Mechanistic studies demonstrate that C−O coupling utilizing L8 ⋅ Cu involves rate‐limiting alkoxide transmetallation, resulting in a mechanism of C−O bond formation that is distinct from previously described Pd‐, Cu‐, or Ni‐based systems. This lower energy pathway leads to rapid C−O bond formation; a 7‐fold increase relative to what is seen with other ligands. The results presented in this report overcome limitations in previously described C−O coupling methods and introduce a new ligand that we anticipate may be useful in other Cu‐catalyzed C‐heteroatom bond‐forming reactions. A room‐temperature Cu‐catalyzed C−O coupling method has been developed utilizing a new N1,N2‐diarylbenzene‐1,2‐diamine ligand. These reactions feature mild reaction conditions, no need to use excess alcohol, and a unique mechanism that does not feature rate‐determining reductive elimination.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202400333