The synthetic utility of 2‐trifluoromethyl‐1H‐pyrrole as a pharmaceutically relevant platform was demonstrated by the preparation of mono‐ and bifunctional C‐2(5)‐ or C‐3‐substituted derivatives, i.e. regioisomeric sulfonyl halides, carboxylic acids, aldehydes, and nitriles. A series of modifications relied on lithiation or electrophilic substitution, which proceeded regioselectively on multigram scale, mostly in protecting‐group‐free mode. Subsequent catalytic hydrogenation of the pyrrole ring was also performed for synthesis of all isomeric 2‐trifluoromethyl α‐ and β‐prolines. These derivatives were considered as promising low‐molecular‐weight building blocks for synthesis, drug discovery, and agrochemistry.

Synthetic approach to fused azasultams with 1,2,4-thiadi­azepine framework via base promoted protocols has been developed. 1H-Azole-2-carboxylates and N-(chloromethyl)-N-methylmethanesulfonamide were used as ambiphilic building blocks in the one-pot and two-step reaction sequences. Chemical behavior of the obtained azasultams in reactions with amines, hydrazine, DMFDMA, and NaBH4 was investigated. An enamino ketone derived from an azasultam was exploited in the synthesis of new pyrazole and pyrimidine heterocycles.

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