Communication
ChemComm
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Scheme 4 Intermolecular competition experiments.
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Scheme 5 Intermolecular competition experiments.
experiments demonstrate no product formation in the attempted
hydroarylation of 1b using the RuH2CO(PPh3)3 catalyst,11 indicat-
ing the superior activity of the in situ generated catalyst. Further
studies to elucidate the mechanism are ongoing.
In conclusion, we have reported the first Ru(0)-catalyzed ketone-
directed hydroarylation of alkynes with a broad substrate scope
by in situ generation of a Ru(0) catalyst from a bench-stable,
commercially-available Ru(II) precursor. Firstly, the method pro-
vides straightforward access to a wide array of functionalized
ketone building blocks under mild reductive conditions by weak
coordination. Secondly, and most crucially, this report documents
that the in situ generated Ru(0) catalysts enable C–H activation of
substrates that would otherwise be unreactive. Given the economic
advantages of Ru(0) catalysis, we anticipate that many new C–H
activation substrates will be amenable to this strategy. Studies to
expand the scope of this strategy will be forthcoming.
Financial support was provided by Rutgers University. The
Bruker 500 MHz spectrometer used in this study was supported
by the NSF-MRI grant (CHE-1229030).
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