We describe here a controlled approach to C1‐symmetrical cyclotriveratrylenes (CTVs). In this approach dimers are synthesized through Barluenga boronic coupling (BBC) and after borylation, the last aromatic ring is introduced by a second BBC. After functional transformations of the trimers, the CTVs are formed using intramolecular SEAr.
The synthesis of undescribed b‐aminodifluoroethylsulfinates and their uses in the hydroaminodifluoroalkylation of alkenes is reported. This reaction is performed in the presence of a photocatalyst (4CzIPN, Ru complexes) and enables the direct incorporation of a b‐difluoroamine moiety onto vinylic aryls, unactivated alkenes, and electron–rich, or –deficient alkenes. The mechanism was studied and the formation of a gem‐difluoromethyl radical is observed after the selective oxidation of the sulfinate function.
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