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6-Arylpurines have been identified with a variety of valuable biological properties, such as anti-mycobacterial, cytostatic, and anti-HCV activities. Therefore, selectively constructing functional 6-arylpurines is significant for emergency. It is well-known, 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. However, metal-catalyzed direct C-H functionalization of 6-arylpurines is rare. Previously, we have elaborated an efficient approach for direct CF3-carbenoid C-H functionalization of (hetero)arenes, indoles and indolines using readily available methyl-3,3,3-trifluoro-2-diazopropionate as a cross-coupling partner under chelation-controlled Ru(III)-catalysis. Herein, we wish to disclose our recent results on the direct Rh(III)-catalyzed CF3-carbenoid functionalization of 6-aryl purines.