Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl HalidesCitation formats

  • External authors:
  • Marco Simonetti
  • Xacobe C. Cambeiro
  • Francisco Julia-Hernandez
  • Jude N. Arokianathar
  • Igor Larrosa

Standard

Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides. / Simonetti, Marco; Perry, Gregory J. P.; Cambeiro, Xacobe C.; Julia-Hernandez, Francisco; Arokianathar, Jude N.; Larrosa, Igor.

In: American Chemical Society. Journal, Vol. 138, No. 10, 2016, p. 3596-3606.

Research output: Contribution to journalArticle

Harvard

Simonetti, M, Perry, GJP, Cambeiro, XC, Julia-Hernandez, F, Arokianathar, JN & Larrosa, I 2016, 'Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides', American Chemical Society. Journal, vol. 138, no. 10, pp. 3596-3606. https://doi.org/10.1021/jacs.6b01615

APA

Simonetti, M., Perry, G. J. P., Cambeiro, X. C., Julia-Hernandez, F., Arokianathar, J. N., & Larrosa, I. (2016). Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides. American Chemical Society. Journal, 138(10), 3596-3606. https://doi.org/10.1021/jacs.6b01615

Vancouver

Simonetti M, Perry GJP, Cambeiro XC, Julia-Hernandez F, Arokianathar JN, Larrosa I. Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides. American Chemical Society. Journal. 2016;138(10):3596-3606. https://doi.org/10.1021/jacs.6b01615

Author

Simonetti, Marco ; Perry, Gregory J. P. ; Cambeiro, Xacobe C. ; Julia-Hernandez, Francisco ; Arokianathar, Jude N. ; Larrosa, Igor. / Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides. In: American Chemical Society. Journal. 2016 ; Vol. 138, No. 10. pp. 3596-3606.

Bibtex

@article{1f7b722e02374403938756f44a9c73f3,
title = "Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides",
abstract = "Although the ruthenium-catalyzed C–H arylation of arenes bearing directing groups with haloarenes is well-known, this process has never been achieved in the absence of directing groups. We report the first example of such a process and show that unexpectedly the reaction only takes place in the presence of catalytic amounts of a benzoic acid. Furthermore, contrary to other transition metals, the arylation site selectivity is governed by both electronic and steric factors. Stoichiometric and NMR mechanistic studies support a catalytic cycle that involves a well-defined η6-arene-ligand-free Ru(II) catalyst. Indeed, upon initial pivalate-assisted C–H activation, the aryl-Ru(II) intermediate generated is able to react with an aryl bromide coupling partner only in the presence of a benzoate additive. In contrast, directing-group-containing substrates (such as 2-phenylpyridine) do not require a benzoate additive. Deuterium labeling and kinetic isotope effect experiments indicate that C–H activation is both reversible and kinetically significant. Computational studies support a concerted metalation–deprotonation (CMD)-type ruthenation mode and shed light on the unusual arylation regioselectivity.",
author = "Marco Simonetti and Perry, {Gregory J. P.} and Cambeiro, {Xacobe C.} and Francisco Julia-Hernandez and Arokianathar, {Jude N.} and Igor Larrosa",
year = "2016",
doi = "10.1021/jacs.6b01615",
language = "English",
volume = "138",
pages = "3596--3606",
journal = "American Chemical Society. Journal",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "10",

}

RIS

TY - JOUR

T1 - Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides

AU - Simonetti, Marco

AU - Perry, Gregory J. P.

AU - Cambeiro, Xacobe C.

AU - Julia-Hernandez, Francisco

AU - Arokianathar, Jude N.

AU - Larrosa, Igor

PY - 2016

Y1 - 2016

N2 - Although the ruthenium-catalyzed C–H arylation of arenes bearing directing groups with haloarenes is well-known, this process has never been achieved in the absence of directing groups. We report the first example of such a process and show that unexpectedly the reaction only takes place in the presence of catalytic amounts of a benzoic acid. Furthermore, contrary to other transition metals, the arylation site selectivity is governed by both electronic and steric factors. Stoichiometric and NMR mechanistic studies support a catalytic cycle that involves a well-defined η6-arene-ligand-free Ru(II) catalyst. Indeed, upon initial pivalate-assisted C–H activation, the aryl-Ru(II) intermediate generated is able to react with an aryl bromide coupling partner only in the presence of a benzoate additive. In contrast, directing-group-containing substrates (such as 2-phenylpyridine) do not require a benzoate additive. Deuterium labeling and kinetic isotope effect experiments indicate that C–H activation is both reversible and kinetically significant. Computational studies support a concerted metalation–deprotonation (CMD)-type ruthenation mode and shed light on the unusual arylation regioselectivity.

AB - Although the ruthenium-catalyzed C–H arylation of arenes bearing directing groups with haloarenes is well-known, this process has never been achieved in the absence of directing groups. We report the first example of such a process and show that unexpectedly the reaction only takes place in the presence of catalytic amounts of a benzoic acid. Furthermore, contrary to other transition metals, the arylation site selectivity is governed by both electronic and steric factors. Stoichiometric and NMR mechanistic studies support a catalytic cycle that involves a well-defined η6-arene-ligand-free Ru(II) catalyst. Indeed, upon initial pivalate-assisted C–H activation, the aryl-Ru(II) intermediate generated is able to react with an aryl bromide coupling partner only in the presence of a benzoate additive. In contrast, directing-group-containing substrates (such as 2-phenylpyridine) do not require a benzoate additive. Deuterium labeling and kinetic isotope effect experiments indicate that C–H activation is both reversible and kinetically significant. Computational studies support a concerted metalation–deprotonation (CMD)-type ruthenation mode and shed light on the unusual arylation regioselectivity.

U2 - 10.1021/jacs.6b01615

DO - 10.1021/jacs.6b01615

M3 - Article

VL - 138

SP - 3596

EP - 3606

JO - American Chemical Society. Journal

JF - American Chemical Society. Journal

SN - 0002-7863

IS - 10

ER -