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COMMUNICATION
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from complex 4 followed by hydride abstraction to form a free
aldehyde is unlikely,[19] since aldehyde coordination seems important
for the amidation. We speculate that intermediates B and C can
readily bind aldehyde and hemiaminal due to the lower steric bulk of
the phenyl substitutents as compared to that of tBu groups in
complex 1 and hence complex 3 is more selective towards amidation.
For the manganese catalyzed ester amidation (Table 2), we suggest
that initially coupling of ester and amine to form amide and alcohol
takes place, followed by reaction of the generated alcohol with the
remaining amine to produce amide as described in Scheme 4.
In conclusion, a variety of amides have been synthesized by
two dehydrogenative coupling reactions, involving alcohols and
amines or esters and amines. Both reactions are catalyzed for the
first time by a complex of an earth abundant metal, manganese
complex 3 and base, and generate hydrogen gas as the only
byproduct. Using the alcohol addition complex 4 as catalyst, the
reaction takes place with no added base. These features make
these synthetic methods atom-economical, environmentally benign,
and sustainable.
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Acknowledgements
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Gauvin, ACS Catal. 2017, 7, 2022.
This research was supported by the European Research Council
(ERC AdG 692775). D. M. holds the Israel Matz Professorial Chair of
Organic Chemistry. A.K. is thankful to the Israel Planning and
Budgeting Commission (PBC) for a fellowship. N. A. E.-J. thanks Mr.
Armando Jinich for a postdoctoral fellowship.
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Keywords: Manganese• amides• dehydrogenative coupling•
pincer•
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