Pd-Catalyzed Fluorocarbonylation of Iodoarenes with Difluoromethyl Benzoates
Hao Zhang1, Ran Liu1, Mingyou Hu1
1State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.
Abstract:
Palladium-catalyzed fluorocarbonylation of iodoarenes using difluoromethyl benzoate (DFBz) or difluoromethyl p-cyano-benzoate (DFBz-CN) as a fluorocarbonylation reagent has been developed, affording structurally diverse acyl fluorides as products. Both DFBz and DFBz-CN reagents are conveniently prepared through insertion of difluorocarbene into the O-H bonds of carboxylic acids. The activation of these two difluoromethyl benzoates with CsF generates formyl fluoride (HCOF), which readily decomposes into CO and HF. Therefore, both DFBz and DFBz-CN can be successfully used as safe surrogates of CO. This study provides not only a new synthetic method for fluorocarbonylation but also intriguing insights into the different reactivity between the previously known trifluoromethyl benzoate (TFBz, an effective CF3O- synthon) and the currently studied difluoromethyl benzoate (DFBz, not a satisfactory HCF2O- synthon).
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