10.1002/anie.202011161
Angewandte Chemie International Edition
RESEARCH ARTICLE
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Acknowledgements
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The authors thank BASF and NIH (R35GM130387) for support
of this work along with the Small Molecule X-ray Crystallography
Facility (S10-RR027172), the Central California 900 MHz NMR
Facility (NIH-GM68933), the College of Chemistry Nuclear
Magnetic Resonance Facility (NIH S10-OD024998), and the
Catalysis Facility of Lawrence Berkeley National Laboratory,
which is supported by the Director, Office of Science, of the US
Department of Energy under contract no. DE-AC02-05CH11231.
The authors thank Dr. Nicholas Settineri for X-ray
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the desired hydrazine under [Pd(cinnamyl)Cl]2 and MorDalPhos catalytic
conditions. For details, see ref. 6a.
Keywords: palladium • transition-metal catalysis • cross-
coupling • aryl halide • hydrazine
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3,5-dimethylpyrazole and an aryl halide, thereby providing a false
positive result, a control reaction with 3,5-dimethylpyrazole, instead of
hydrazine, and chlorobenzene was performed (see Supporting
Information for details), and the N-aryl pyrazole was not detected by 1
H
NMR spectroscopy or GC-MS analysis. Thus, the pyrazoles formed by
the reactions in Table 2 result from the condensation of the aryl hydrazine
with acetylacetone and not by a C–N coupling reaction between an aryl
halide and 3,5-dimethylpyrazole.
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condensation of hydrazine onto the ketone in 1h under basic conditions
during the course of the reaction of the hydrazine product and
acetylacetone.
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[24] The reaction represented by the circle trace in Figure 4 was conducted
in an NMR tube. Because this heterogeneous reaction was not stirred,
the rate of this reaction is expected to be even faster with stirring, as in
the case of the catalytic reaction.
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[26] More quantitatively, the decomposition of aryl hydroxide 5 at 100 °C in a
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