Room‐Temperature Copper‐Catalyzed Etherification of Aryl Bromides
Name
Angew Chem Int Ed - 2024 - Strauss - Room‐Temperature Copper‐Catalyzed Etherification of Aryl Bromides.pdf
Size
7.15 MB
Format
Adobe PDF
Checksum (MD5)
835b0817b03384ec89219e2787e35e7d
Author(s)
Strauss, Michael J
Greaves, Megan E
Kim, Seoung‐Tae
Teijaro, Christiana N
Schmidt, Michael A
Scola, Paul M
Buchwald, Stephen L
Date Issued
February 15, 2024
Journal
Angewandte Chemie International Edition
Publisher
Wiley
Citation
M. J.Strauss, M. E.Greaves, S.-T.Kim, C. N.Teijaro, M. A.Schmidt, P. M.Scola, S. L.Buchwald, Angew. Chem. Int. Ed.2024, 63, e202400333.
Version
Final published version
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-NonCommercial-NoDerivatives
Persistent DSpace Link
DOI of Published Version
10.1002/anie.202400333
