10.1002/anie.201710698
Angewandte Chemie International Edition
COMMUNICATION
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Figure S7-9). These observations shed new light on the
hypothesized mechanism (Scheme 1B): the excited
photocatalyst PC* oxidizes DIPEA to form the PC- and DIPEA·+ ,
and the latter oxidizes Ni(II) to Ni(III) while the former reduces
the Ni(I) to Ni(0) following reductive elimination to form the
phenol product at the Ni(III) center. However, direct oxidation of
Ni(II) to Ni(III) by the excited photocatalyst is also possible.[29]
More detailed studies are ongoing in our lab, aiming to
elucidate the role of BODIPY, DIPEA and nickel catalyst.
In summary, we have developed
a nickel-catalyzed
[9] For photocatalytic direct hydroxylation of arenes with water, see: Y.-W.
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Tung, J. Am. Chem. Soc. 2016, 138, 10080.
hydroxylation of aryl halides with water under visible light with
BODIPY as the photocatalyst and DIPEA as the base. This
methodology enables the hydroxylation of a wide range of aryl
bromides and even less-active aryl chlorides with various
functionalities. Together with the use of inexpensive metal
catalyst, organic photosensitizer and organic base, this feature
makes the protocol practically valuable for the synthesis of
phenols.
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Acknowledgements
This research was supported by the National Natural Science
Foundation of China (21372148), the Program for Changjiang
Scholars and the 111 project (B14041).
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Keywords: hydroxylation ·aryl halides ·photoredox catalysis ·nickel
catalysis·BODIPY·
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