10.1002/adsc.202000301
Advanced Synthesis & Catalysis
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Scheme 3. Proposed Reaction Mechanism
In conclusion, we have developed a cobalt-
catalyzed carboxylation of aryl bromides with CO2
under mild conditions. The reaction employs simple
cobalt iodide/2,2′-bpy catalysts, zinc powder as a
reducing reagent, and 1 atm of CO2. Excellent
functional group tolerance is observed, with ester,
chloride, fluoride, trifluoromethyl, ether, thioether,
and amino functionalities tolerated. The mechanism
likely involves the intermediary of ArCoBr species.
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Experimental Section
General
procedure
for
cobalt-catalyzed
carboxylation of aryl bromides with carbon dioxide:
CoI2 (0.05 mmol, 15.6 mg), 2,2'-bipyridine (0.05 mmol,
7.8 mg), Zn powder (2 equiv, 65.4 mg), LiCl (3 equiv, 63.6
mg), 4-methoxy-bromobenzene (0.5 mmol, 93.5 mg),
CH3CN (1.0 mL) and DMF (0.1 mL) were submitted to a
sealed Schlenk tube (25 mL) under the atmosphere of
carbon dioxide. The mixture was cooled to room
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o
temperature after stirring at 40 C for 14 h. Then, HCl (2
M) was added into the tube to quench this reaction. Next,
the combined organic phase extracted with CH2Cl2 (3 × 5
mL) from this reaction was dried by anhydrous MgSO4.
Finally, the corresponding pure product was obtained via
purified by silica gel (petroleum ether/ethyl acetate = 5/1).
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21871163, 91645120, and 21911530097).
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