A HFIP-promoted highly selective hydroxyalkylation of aniline derivatives with arylglyoxal hydrates has been realized. The reaction produces various N,N-dialkylanilines and their derivatives with α-hydroxy carbonyl units in good to excellent yields under mild conditions. Furthermore, the synthetic potential of this method has been demonstrated by the facile synthesis of several structurally interesting molecules such as benzil, 1,2,4-triazine, quinoxaline, hydantoin, and 2-thiohydantoin with aromatic amine units.

A hexafluoroisopropanol (HFIP)-promoted hydroxydifluoromethylation of aniline, indole, and pyrrole derivatives with difluoroacetaldehyde ethyl hemiacetal has been developed. This protocol provides a facile and straightforward approach to access diverse difluoromethylated carbinols in good to excellent yields under mild conditions. Furthermore, gram-scale and synthetic derivatization experiments have also been demonstrated.

A palladium-catalyzed highly regioselective C−H allylation/annulation reaction of N-sulfonyl amides with secondary or tertiary allylic alcohols has been developed to construct 3,4-dihydroisoquinolones bearing a synthetically valuable vinyl substituent. This cascade cyclization approach of allylic alcohols involving C−H allylation has not been reported previously. The commercially available allylic alcohol substrates, the only by-product of water, and the used terminal oxidant of O 2 provide environmentally benign advantages.

A visible light promoted direct benzylic C−H difluoroalkylation with difluoroenoxysilanes has been developed catalyzed by Na2-eosin Y via HAT-ORPC pathway, providing an efficient and atom-economic method for difluoroalkylation of C(sp3)-based...