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The development of new methods for the synthesis of heteroaromatic compounds is an ever-expanding area in bioorganic and medicinal chemistry. At the same time, the significant impact of fluorine functionalities on the modern drug discovery process is well recognized and has been the subject of numerous publications. Therefore, the development of new effective methods for the selective introduction of fluorine and fluorinated groups in (hetero)arenes has a great current interest. On the other hand, in the past decade the transition-metal-catalyzed functionalization of the C–H bond has emerged as one of the most efficient synthetic methods in terms atom-economy to construct diverse organic molecules from simple starting materials. We have recently elaborated an efficient approach for direct CF3-carbenoid C-H functionalization of functionalized benzenes, indoles, indolines and purines under chelation-controlled Rh(III)-catalysis using readily available methyl-3,3,3-trifluoro-2-diazopropionate as a cross-coupling partner.