Recent synthetic methods towards the –OCHF2 moiety

Trifluoromethoxylation Reactions of (Hetero) arenes, Olefinic Systems and Aliphatic Saturated Substrates

“…Ngai and coworkers [67,68] informed the stable reagent 9 (Figure 7), which by SET or homolytic dissociation of the N−O bond generates CF 3 O radicals. Other reports by Ngai, Togni, (reagents 10 and 11 ) and Tang introduced reagents that by SET processes render the CF 3 O radical [16,22,69–73] . The use of these reagents will be discussed in coming sections.…”

“…Reagent 12 (Figure 7) has recently been used in combination with dioxygen to produce the CF 3 O radical (Section 3) [74] . Reagents 9 – 11 (Figure 7) have been discussed and compared in a recent review article [22] …”

“…Cong, Tang, and colleagues [85,19,21,22] reported an azido trifluoromethoxylation reaction of styrene derivatives by concomitant visible‐light mediated photoredox and silver catalysis under mild reaction conditions, with trifluoromethyl arylsulfonate (TFMS) as trifluoromethoxylating reagent [19] . This methodology has been reviewed by Tang [21] and Ngai groups [22] . Scheme 19 illustrates the general protocol for this reaction.…”

“…There are recent review articles on trifluoromethoxylation reactions in the literature, [19–26] whose classifications are based on types of trifluoromethoxylating reagents, [21,26] types of reactions such as nucleophilic, metal‐assisted or catalytic reactions, [19,22] and methodologies based on direct or indirect methods [25] . A classification of trifluoromethoxylation reactions based on distinct families of organic compounds is pertinent and useful for synthetic organic chemists.…”

AlCl3-Mediated CHF2 Transfer and Cyclocondensation of Difluoromethoxy Functionalized o-Phenylenediamines to Access N-Substituted Benzimidazoles

“…Inspired by these facts, in our present study, we assumed that the −NH group of difluoromethoxy functionalized o -phenylenediamine ( 1a ) − can act as a Lewis base, in the presence of Lewis acid AlCl 3 to form FLPs. Furthermore, this pair will cleave the C–F bond, and subsequent transfer of the −CHF 2 group from oxygen to nitrogen via C–O bond cleavage allowed accessing N-substituted benzimidazoles.…”