European Journal of Organic Chemistry
10.1002/ejoc.201700660
COMMUNICATION
In order to enlarge the scope of application of our nickel
catalyst, we encompassed the challenging coupling of primary
aliphatic amines as a particularly significant class of amines for
such cross coupling. To avoid the difficult handling of gaseous
methyl- and ethylamine, the corresponding ammonium chloride
salts were used. Under our standard catalytic conditions, the
monoarylation of methyl- as well as ethylamine occurred with
moderate to good yields and excellent selectivities (Scheme 5).
It should be mentioned that toluene turned out to be a slightly
better solvent for this type of substrates. The reaction was
tolerant to both electron-withdrawing as well as electron-
donating groups. More interestingly, the heterocyclic compound
Keywords: amination • ammonia • arylation • cross-coupling •
nickel
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To
2
demonstrate the introduction of our single component
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3
1
in-situ P-NMR studies indicate the formation of (SL-J003-
2
1
2
)Ni( -NC-Ph-4-NH ) which can readily initiate the catalytic
cycle via subsequent oxidative addition of an aryl electrophile.
In summary, we have identified a Nickel/JosiPhos catalyst
system that has enabled the first examples of ammonia
monoarylation with aryl carbamates. Furthermore, the synthesis
and application of the air-stable single component nickel
precatalyst SK-J003-1n has been described. The efficacy of this
complex has been demonstrated in the coupling of ammonia
from solution or ammonium sulfate. The scope of primary alkyl
amines, employed as their hydrochloride salts, is unprecedented
in amination reactions of aryl carbamates. These findings
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use of halides and sulfonates but also gives access to an
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Additional mechanistic investigation as well as the applicability
of (JosiPhos)Ni(Ph-4-CN)Cl complexes in different cross
coupling processes are ongoing.
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Acknowledgements
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Longchambon) for collecting the crystallographic data and
solving the structure of complex SK-J003-1n.
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