10.1002/anie.202011815
Angewandte Chemie International Edition
COMMUNICATION
This work was supported by the German Science Foundation
(DFG, KO 1537/18-1). This project has received funding from
the European Research Council (ERC) under the European
Union's Horizon 2020 Research and Innovation Programme
(grant agreement No. 741623). We thank Dr. Rudolf Vasold for
GC-MS measurements and Regina Hoheisel for Cyclic
Voltammetry measurements.
excellent yields (Scheme 2, 5-39). Functional groups such as
carboxylic acid, ester, amide, halogens, cyanide and boronic
ester were untouched during the reaction (Scheme 2, 5-6, 9-12,
15-18 and 22-23). Applying this methodology, a dinitrile could
also be synthesized in an one-pot procedure with a moderate
yield (24). Structurally complex, bioactive- and drug- molecules
could be employed for a selective cyanation as well, rendering
the desired product in good to excellent yields up to 76%
(Scheme 2, 29-39). Delightfully, substrates bearing multiple
oxygen atoms, which are usually not stable under photochemical
conditions in the presence of oxygen, are viable, too.[24] Using
the developed protocol, sugar derivatives 29 and 38 were
obtained in 62% and 60% yield, respectively. Further, more
challenging substrates such as cholesterol, isoborneol, amino
acid and peptide derivatives gave the corresponding products in
45-70% yield. Interestingly, anti-inflammatory drug (Celecoxib,
37) gave the desired product in 70% yield. For the example of a
Keywords: Photoredox catalysis• nitriles• C-H functionalization•
methylarenes• ammoxidation •
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2 and Celecoxib were
cyanated in a 1 g scale to give the desired product in 65 and
60% yield respectively (Scheme S1). After the screening of
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the synthesis of aromatic nitriles as well (Scheme 3). Similar to
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Sterically crowded 2,6-dichlorobenzaldehyde (Scheme 3) was a
viable substrate, too, giving 2,6-dichlorobenzonitrile (DCBN, 45)
in 82% yield, which is used as herbicide and regarded as a
potential intermediate for pesticides and agrochemicals.
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In conclusion, we present the first metal- and cyanide-free
visible-light-induced photocatalytic ammoxidation of C(sp3)-H
bonds using an abundant ammonia source and molecular
oxygen. A detailed mechanistic investigation was carried out to
support the proposed mechanistic hypothesis including various
spectroscopy experiments. Applying this methodology, more
than 50 aromatic and heteroaromatic substrates, as well as
steroids and existing drug molecules containing methyl groups
could be converted to the nitrile in good to excellent yields. In
addition to this, the method could be executed on gram scale
and alcohols, aldehydes and oximes could be used as starting
materials for their conversion to nitriles in up to 91% yield in the
same manner.
Associated content
[3]
Supporting Information. The Supporting Information is
available free of charge on the Angewandte Chemie
Publications website at. Contains complete experimental
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procedures
including
general
considerations
and
characterization data and NMR spectra.
Notes
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The authors declare no competing financial interest.
Acknowledgements
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