Selective Synthesis of Cyclic Nitroene‐Sulfonamides from Aliphatic Sulfamides and NOBF₄

Abstract

Described herein is the development of a desaturation and N-βnitration reaction of cyclic amides, which is achieved by a selective hydrogen atom transfer (HAT)/oxidative desaturation/ electrophilic nitration process. In this procedure, di-tert-butyl peroxide (DTBP) acted both as the oxidant and HAT reagent, and electrophilic NOBF 4 as nitration source. Notably, the application of produced cyclic nitroene-sulfonamides was showcased by their efficient transformations into 3-piperidones and poly-substituted piperidine derivatives.

Visible-light-induced dehydrogenative β-trifluoromethylthiolation of tertiary amines and direct β-trifluoromethylthiolation of enamides

“…Given the increasing prevalence of the trifluoromethylthio group in medicinal chemistry 11 and our continued pursuit of innovative methodologies for β-functionalization of saturated heterocycles, 12 we envisioned that tertiary amines could establish an EDA complex with electrophilic N-SCF 3 reagent via π–π stacking interaction. This is evidenced by the atomic distance (3.16 Å) between the closest carbon atoms of the respective rings (see the simulated structure in Scheme 1c).…”

Silver-catalyzed nitrosation and nitration of aromatic amides using NOBF4

“…Recently, our group exploited a desaturation and N -β-nitration reaction of cyclic amides using electrophilic NOBF 4 as a nitration source. 9 In this context, we hope to further exploit an efficient approach for the nitrosation of aromatic amides on the benzene ring. In order to avoid the possible competitive nitrosation on the N atom of amides, herein, we successfully developed a coordination activation strategy 10 for the nitrosation of arylamides using AgNO 3 as the catalyst and NOBF 4 as the electrophile (Scheme 1c).…”