Efficient Direct Alkynylation of Trifluoromethyl Ketones Catalyzed by AgF in Water and Organic Solvents

Guo-Jun Deng; Chao-Jun Li

doi:10.1055/s-2008-1078421

CLUSTER

Efficient Direct Alkynylation of Trifluoromethyl Ketones Catalyzed by AgF in Water and Organic Solvents

Guo-Jun Deng^a, Chao-Jun Li*^a,b
^a Department of Chemistry, Tulane University, New Orleans, LA, 70118, USA
^b Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, QC, H3A 2K6, Canada
Fax: +1(514)3983797; e-Mail: cj.li@mcgill.ca;

Abstract

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Abstract

A general and efficient method for the direct alkynylation of trifluoropyruvate and trifluoroacetophenone in water was developed by using AgF and PCy₃ as a catalyst. The ligand enhanced the catalyst activity significantly. The reaction in water is comparable to the one carried out in organic solvents.

Key words

direct alkynylation - trifluoromethyl ketones - silver fluoride

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References

References and Notes

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Representative Experimental Procedure
A nitrogen-flushed 10 mL flask equipped with a magnetic stirrer and a septum was charged with AgF (6.3 mg, 0.05 mmol) and PCy₃ (14 mg, 0.05 mmol). Ethyl 3,3,3-trifluoro-pyruvate (85 mg, 0.5 mmol), alkyne (2 equiv), and H₂O (0.5 mL) were added by using a syringe. The reaction mixture was stirred for 1-2 d at r.t. and extracted with Et₂O. The organic solvent was evaporated and the residue was purified by column chromatography (SiO₂, hexane-EtOAc) and characterized by means of ¹H NMR, ¹³C NMR, IR, and HRMS.