Photoredox-catalyzed direct C–H monofluoromethylation of heteroarenes

Abstract

Fluoroalkyl groups play a vital role in pharmaceutical products and agrochemicals, where their installation onto aryl and heterocyclic rings can often lead to enhanced physicochemical and biological properties. Among them,...

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

“…[107] Additionally, [bis(monofluoroacetoxy)iodo]-benzene reagent ( 17) has emerged as a convenient source for generating monofluoromethyl radicals under photoredox catalysis (B). [108] Substrate scope: * CHFR is a family encompassing radical with varied philicity depending on the R substituent, from nucleophilic (CH 2 F, ω = 1.08 eV, ω À = 0.30 eV) to electrophilic character for R=EWG (ω = 1.38-1.70 eV, ω À = 0.23-0.26 eV). This description is in line with the observable chemical space, where the addition of * CH 2 F radicals is mainly reported for e-poor aromatics while that of * CHF-EWG radicals is documented largely for e-rich aromatics (Figure 16).…”

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

“…In this context, the Dong group has leveraged the capabilities of reagent 16 by utilizing it in a silver‐catalyzed process ( E ), thus enabling the direct monofluoroalkylation of heteroarenes [107] . Additionally, [bis(monofluoroacetoxy)iodo]‐benzene reagent ( 17 ) has emerged as a convenient source for generating monofluoromethyl radicals under photoredox catalysis ( B ) [108] …”

NHC and photoredox catalysis dual-catalyzed 1,4-mono-/di-fluoromethylative acylation of 1,3-enynes

“…Significant progress has been achieved in radical fluoroalkylation, including trifluoromethylation, 4 difluoromethylation, 5–7 and others. However, in terms of radical monofluoromethylation 8–12 of C–C multiple bonds, it still appears to be in its infancy. In this domain, monofluoromethylation of olefins 9,10 is relatively well-documented, and the transformation includes hydro-monofluoromethylation, 9 chloro-monofluoromethylation, 10 a oxy-monofluoromethylation, 10 b – d etc.…”