N-Fluorobenzenesulfonimide: a useful and versatile reagent for the direct fluorination and amination of (hetero)aromatic C–H bonds

Abstract

This review updates recent advances and developments in the direct fluorination and amination of (hetero)aromatic C–H bonds utilizing N-fluorobenzenesulfonimide, classified according to the type of catalyst.

Reactivities of electrophilic N–F fluorinating reagents

“…Here, NFSI 23 shows practicable reactivity towards aldehyde substrates in the presence of an organocatalyst, and this is also mirrored by its many synthetic applications in metal catalysed reactions. 142,143 In 2020, Cornella et al 144 reported the electrophilic fluorination of arylboronic esters enabled by bismuth redox catalysis. The reactivities of several N−F reagents with phenylbismine 167 were investigated ( 144 Yields were determined by 19 F NMR spectroscopic analysis of crude reactions using 1-fluoro-4-nitrobenzene as an internal standard.…”

Multi-faceted reactivity of N-fluorobenzenesulfonimide (NFSI) under mechanochemical conditions: fluorination, fluorodemethylation, sulfonylation, and amidation reactions

“…In the search for solid reagents compatible with mechanochemical techniques, we became interested in evaluating the behavior of N -fluorobenzenesulfonimide (NFSI) under ball-milling conditions. NFSI is a colorless crystalline powder (mp 114–116 °C), bench-stable, and an easy-to-handle reagent, which, due to its commercial availability, has been extensively used as a fluorinating agent in solution [ 7 – 9 ]. Additionally, NFSI has also been explored as an oxidant, amidation reagent [ 9 – 11 ], and phenylsulfonyl group transfer reagent [ 12 – 13 ].…”

“…NFSI is a colorless crystalline powder (mp 114–116 °C), bench-stable, and an easy-to-handle reagent, which, due to its commercial availability, has been extensively used as a fluorinating agent in solution [ 7 – 9 ]. Additionally, NFSI has also been explored as an oxidant, amidation reagent [ 9 – 11 ], and phenylsulfonyl group transfer reagent [ 12 – 13 ].…”

Synthesis of Fluorinated 3,6-Dihydropyridines and 2-(Fluoromethyl)pyridines by Electrophilic Fluorination of 1,2-Dihydropyridines with Selectfluor®

“…The electrophilic fluorination of aromatic heterocycles has been less studied than the fluorination of arenes. However, a number of fluoropyrroles [ 4 , 5 ], furans [ 6 ], thiophenes [ 7 ], pyrrolo[2,3-d]pyrimidines [ 8 , 9 ], quinolines [ 10 , 11 , 12 ] and indoles [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ] have been prepared either by direct fluorination or by fluorodecarboxylation using mainly Selectfluor ® and N -fluorobenzenesulfonimide.…”