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Scheme 2 Results of the N-formamide intermediates during the
N-methylation of different amines catalyzed by 2 wt% Pd/CuZrOx.
amines, i.e. 1,2,3,4-tetrahydroisoquinoline, 4-ethylpiperidine and
dodecylamine, were used as the starting materials to test the
aforementioned hypothesis (Scheme 2). Hence, the corresponding
N-formamides intermediates, i.e. 9c, 7c and 23c, can be synthesized
with 56–68% isolated yields when the reactions were carried out
with 15 h. Regarding the N-formamide, we expectꢁed that it was
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generated via carbenium ion intermediate ðRNH C ¼ OÞ, which
was formed through the dehydration of carbamic acid (RNHCO2H),
and a detailed description of the reaction mechanism is given in
the ESI† in Fig. S6.
In conclusion, an active Pd/CuZrOx catalyst for the reductive
amination of CO2 using molecular hydrogen as a reducing agent was
prepared by varying the composition of metal oxide supports. In the
presence of this catalyst, the N-methylation reactions of amine and
nitro compounds can be carried out smoothly under relatively mild
reaction conditions without any additional co-catalyst. N-Methyl or
N,N0-dimethyl amines with various structures can synthesized with
yields of up to 97%. N-Formylation becomes the main reaction if the
reaction was performed under milder conditions or using Pd/ZnZrOx
as a catalyst. These results should be valuable for the development of
a novel catalyst for CO2 activation under mild conditions.
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´
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