The difluoromethyl group (CFH) is of great interest in the area of medicinal chemistry. However, the investigation of molecular scaffolds containing this group has been hampered by the limitation of synthetic methods for the introduction of CFH into heteroarenes. Herein we disclose a new strategy for the direct introduction of a difluoromethyl group into heteroarenes via the copper-mediated C-H oxidative difluoromethylation of heteroarenes with TMSCFH. This mild and regioselective method enables the convenient synthesis of a range of difluoromethylated heteroarenes in high yields. The usage of 9,10-phenanthrenequinone (PQ) as an oxidant is critical to the success of this new difluoromethylation reaction.

A tandem ring‐opening and deoxytrifluoromethylthiolation of aromatic epoxides with AgSCF3 and nBu4NI/KI has been developed. This protocol provides a convenient access to a series of novel 1,2‐bis(trifluoromethylthiolated) products, which has been rarely reported and might find applications in medicinal and material chemistry.

A deoxygenative 1,1-bis-trifluoromethylthiolation of readily available aromatic aldehydes with AgSCF 3 in the presence of KI and (NH 4) 2 SO 4 was established. This reaction delivered a series of bis(trifluoromethylthio)methylarenes in moderate to high yields. The precise control of the generation and decomposition of SCF 3 anion is the key to the successful transformation.

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