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Milner PJ, Yang Y, Buchwald SL. In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides. Organometallics. 2015;34(19):4775-4780doi: 10.1021/acs.organomet.5b00631.
Milner, P. J., Yang, Y., & Buchwald, S. L. (2015). In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides. Organometallics, 34(19), 4775-4780. https://doi.org/10.1021/acs.organomet.5b00631
Milner, Phillip J, et al. "In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides." Organometallics vol. 34,19 (2015): 4775-4780. doi: https://doi.org/10.1021/acs.organomet.5b00631
Milner PJ, Yang Y, Buchwald SL. In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides. Organometallics. 2015 Oct 12;34(19):4775-4780. doi: 10.1021/acs.organomet.5b00631. Epub 2015 Aug 20. PMID: 27056379; PMCID: PMC4820280.
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Organometallics. 2015 Oct 12;34(19):4775-4780. doi: 10.1021/acs.organomet.5b00631. Epub 2015 Aug 20.

In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides.

Organometallics

Phillip J Milner, Yang Yang, Stephen L Buchwald

Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
  2. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States; Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.

PMID: 27056379 PMCID: PMC4820280 DOI: 10.1021/acs.organomet.5b00631

Abstract

A thorough investigation of the challenging Pd-catalyzed fluorination of five-membered heteroaryl bromides is presented. Crystallographic studies and density functional theory (DFT) calculations suggest that the challenging step of this transformation is C-F reductive elimination of five-membered heteroaryl fluorides from Pd(II) complexes. On the basis of these studies, we have found that various heteroaryl bromides bearing phenyl groups in the ortho position can be effectively fluorinated under catalytic conditions. Highly activated 2-bromoazoles, such as 8-bromocaffeine, are also viable substrates for this reaction.

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