Palladium-Catalyzed Reductive Carbonylation of Aryl Triflates with Synthesis Gas

Abstract

A general palladium-catalyzed reductive carbonylation of aryl triflates in the presence of synthesis gas (CO/H₂) has been developed. The reaction with this most simple and environmentally benign formylation source proceeds under mild conditions and various aromatic aldehydes have been prepared in good to high yield.

Key words

carbonylation - palladium - aryl triflates - aldehydes - homogenous catalysis

References and Notes

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18

A 50 mL round-bottom flask was charged with 4-methoxy-phenol (1.86 g, 15 mmol) and sealed with a septum. Subsequently, pyridine (15 mL) was added. The clear solution was cooled to 0 °C and trifluoromethanesulfonic anhydride (2.8 mL, 17 mmol) was added dropwise. The resulting orange solution was stirred over night at r.t. Another 10 mL Schlenk flask was charged with Pd(OAc)₂ (50.5 mg, 1.5 mol%), 1,3-bis(diphenylphosphino)propane (139.2 mg, 2.25 mol%), DMF (5 mL), and 2-butoxyethyl ether (2.61 mL, internal GC standard). Both solutions were combined and transferred to a 100 mL autoclave of the 4560 series from Parr Instruments^® under argon atmosphere. After flushing the autoclave three times with CO/H₂ (1:1), 20 bar of synthesis gas were adjusted at ambient temperature and the reaction was performed for 24 h at 100 °C. Before and after the reductive carbonylation an aliquot of the reaction mixture was subjected to GC analysis for determination of yield and conversion.