Although the pentafluorosulfanyl group was regarded as a “substituent of the future” due to its unique structural and electronic features and potential medicinal properties, there are still a very limited number of methods to accesses SF₅-containing heterocycles. Herein, we present an efficient one-pot tandem SF₅-quinoline synthetic method. Iron(III) was employed as the catalyst for the three-component coupling reaction of SF₅-anilines, aldehydes and alkynes. The reaction was performed in the presence of air and a series of 6- or 7-SF₅-substituted quinolines were obtained in good yields.

Chemoselective control over N/O selectivity is an intriguing issue in nitroso chemistry. Recently, we reported an unprecedented asymmetric α-amination reaction of β-ketocarbonyl compounds that proceeded through the catalytic coupling of enamine carbonyl groups with in-situ-generated carbonyl nitroso moieties. This process was facilitated by a simple chiral primary and tertiary diamine that was derived from tert-leucine. This reaction featured high chemoselectivity and excellent enantioselectivity for a broad range of substrates. Herein, a computational study was performed to elucidate the origins of the enantioselectivity and N/O regioselectivity. We found that a bidentate hydrogen-bonding interaction between the tertiary N⁺H and nitrosocarbonyl groups accounted for the high N selectivity, whilst the enantioselectivity was determined by Si-facial attack on the (E)- and (Z)-enamines in a Curtin–Hammett-type manner. The bidentate hydrogen-bonding interaction with the nitrosocarbonyl moieties reinforced the facial selectivity in this process.