Journal of the American Chemical Society
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by 19F NMR of the stoichiometric reactions between 4-FC6H4ZnI
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and AgBF4, and between 4-FC6H4ZnI and CuI showed that there
were no reactions, and that [Ar-Ag] and [Ar-Cu] species were not
generated. These experiments indicated that, unlike diarylzinc
reagents (Ar2Zn), monoarylzinc reagents (ArZnX) do not react
with Ag and Cu-salts under our reaction conditions and that the
current ,-alkene diarylation reaction was not promoted by a
sequential Zn to Ag/Cu to Ni transmetalation. Therefore, the cata-
lytic cycles C and D are unlikely to be operative for this process.
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Scheme 4. 19F NMR monitoring of the reactions between ArZnI
and AgBF4, and ArZnI and CuI.
In summary, we have developed new synergistic bimetallic Ni/Ag
and Ni/Cu catalysts for regioselective diarylation of unactivated
alkenes located at the ,-position of ketimines. The reaction, after
simple H+ workup, furnishes ,-diarylketones in good yields. The
synergistic Ni/Ag and Ni/Cu catalytic systems generate cationic
Ni(II)-species in situ by abstracting halides (X−) from Ar-Ni-X
species. In situ monitoring of reaction progress by 19F NMR indi-
cates that the cationic Ni-catalyst promotes the migratory inser-
tion and transmetalation steps, and suppresses -H elimination,
the fundamental process that causes significant problems during
alkene difunctionalization. We believe that this new approach of
synergistic bimetallic cationic catalytic systems will stimulate
further research in solving problems in alkene difunctionalization
reactions.
ASSOCIATED CONTENT
Supporting Information
Experimental procedures and characterization data for all
compounds. This material is available free of charge via the
Crystallographic data for ±41-DNP can be found at CCDC
deposition number 1871839.
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AUTHOR INFORMATION
Corresponding Author
(8) For Ni-catalyzed Heck reactions, see: (a) Matsubara, R.; Gutierrez,
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Desrosiers, J.-N.; Hie, L.; Biswas, S.; Zatolochnaya, O. V.; Rodriguez, S.;
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Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
We thank the University of New Mexico (UNM) and the
National Science Foundation (NSF CHE-1554299) for fi-
nancial support, and upgrades to the NMR (NSF grants
CHE08-40523 and CHE09-46690) and MS Facilities. The
Bruker X-ray diffractometer was purchased via an NSF
CRIF:MU award to UNM (CHE04-43580). We thank Pro-
fessor Emeritus Roger E. Cramer, University of Hawaii, for
help with X-ray crystallography. Sandia National Laborato-
ries (See the SI).
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