10.1002/asia.202100540
Chemistry - An Asian Journal
COMMUNICATION
Acknowledgements
We acknowledge the financial support the Joint Funds of
Zhejiang Natural Science Foundation and Taizhou
(LTY21B020001).
Keywords: Palladium catalysis • Carbonylation • Suzuki
coupling • Ketone • Heterogeneouscatalyst
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Scheme 4 Proposed mechanism.
On the basis of previous reports,[2,3] a plausible mechanism
is proposed as shown in Scheme 4. At first, oxidative addition of
Pd0 to Ar-Br provides the Ar-Pd II-Br complex A. Next, CO
insertion into the Pd-C bond of A leads to the formation of ArCO-
Pd-Br intermediate B. Then, nucleophilic addition of arylboronic
acid to B generates the species C. Finally, reductive elimination
of C affords the product 3a and regenerates the active Pd0
speciesforthe next catalyticcycle.
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In conclusion, we have developed
a
facile and
straightforward approach to prepare diaryl ketones via a
heterogeneous palladium-catalyzed carbonylative Suzuki cross-
coupling of aryl bromides and arylboronic acids using TFBen as
the CO source.
[4]
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Experimental Procedure
Catalyst preparation
g-C3N4 was obtained by a typical method.[8] The
synthesis of Pd/g-C3N4 underwent two procedures. First, g-
C3N4 was dispersed in N,N-dimethylformamide (DMF) and
sonicated for several hours. The ultrasonicated g-C3N4
reacted with isonicotinoyl chloride hydrochloride (INCH) in
DMF mixed with several drops of triethylamine (TEA) at
60°C for 6 h. The reacted solution was centrifuged, washed
and freeze-dried to obtain g-C3N4-INCH. g-C3N4-INCH and
PdCl2 were mixed well in aqueous solution and refluxed for
at 60°C. After reacting, the products were washed with
DMF and ultra-pure water several times and Pd/g-C3N4 was
obtained by freeze-drying.
General procedure forcarbonylative Suzuki cross-coupling
Aryl bromides 1 (0.2 mmol, 1.0 equiv), arylboronic acids 2
(0.4 mmol, 2.0 equiv), Pd/g-C3N4 (7.9 mg, 0.01 mmol, 5 mol%),
BuPAd2 (10 mol%), and a 1.5 mL vial containing TFBen (210.0
mg, 1.0 mmol, 5.0 equiv) were added to an oven-dried tube
(15.0 mL) which was then placed under vacuum and refilled with
nitrogen three times. Then NEt3 (2.0 equiv) and THF (1.0 mL)
were added into the tube via syringe. The tube was sealed and
stirred at 100 °C for 16 h. Upon the reaction was completed, the
resulting mixture was concentrated under vacuum and purified
by silica gel column using chromatography (petroleum ether /
ethyl acetate =20:1) to obtain diaryl ketones 3.
[7]
[8]
For a review on carbonylative transformation of aryl chlorides and
tosylates, see: X.-F. Wu, RSCAdv. 2016, 6, 83831-83837.
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2011, 21, 15171-15174.
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