Interaction of α,α-difluoroazides with trivalent phosphorus compounds and triphenylantimony

Synthesis, Stability and Reactivity of α‐Fluorinated Azidoalkanes

“…[4] The substitution reactionc an be performed also on halodifluorinated acetates, acetamides or acetophenones (Scheme 2). [5][6][7][8] The reactions might operate through an S RN 1m echanism.D olbier and co-workers have recently studied the influenceo ff luorine substituent on the rate of nucleophilic substitution and elimination in aliphatic compounds. For alkyl bromides the order of reactivity with sodium azide in MeOH at 50 8Cw as (relativer ates): RCH 2 Br (1) > RCHFBr (0.2) @ RCF 2 Br (8 10 À5 ,n oreaction).…”

“…[43] The general schemeo fr eaction of fluoroalkylated azides with P III compounds is depicted in Scheme 33. [8,13,[44][45][46][47] Initially,p hosphazides form. They are generally unstable and decompose to iminophosphoranes.…”

“…[47,48] Triphenylantimony and diphenyltellurium react with fluorinated azidesa te levated temperature in an analogouso xidative fluorination process to afford the corresponding difluorides (Scheme 35). [8,47,49] Scheme29. Synthesis of 5-iodo triazoles and 4,5-disubstituted triazoles.…”

Synthesis of tetrafluoroethylene- and tetrafluoroethyl-containing azides and their 1,3-dipolar cycloaddition as synthetic application

“…In the latest report, tetrafluoroethyl bromides were reacted with i-PrMgCl•LiCl to afford metalated species stable at low temperature and displaying excellent reactivity with a range of electrophiles with one example of an electrophilic azide. 32 Azides are highly valuable compounds in organic synthesissome fluoroalkyl azides are known, [33][34][35][36][37][38][39][40] including CF 3 N 3 41,42 and perfluoroalkyl analogues for which we have recently reported a new and practical synthetic method. 43 Perfluoroalkyl azides were investigated in copper(I)catalyzed azide-alkyne cycloadditon (CuAAC) [44][45][46] furnishing N-perfluoroalkyl-1,2,3-triazoles.…”

Azidoperfluoroalkanes: Synthesis and Application in Copper(I)‐Catalyzed Azide–Alkyne Cycloaddition

“…Some azidopolyfluoroalkanes have been synthesized through the reaction of sodium azide with polyfluoroalkenes [11] or halodifluoromethyl compounds. [12] Optimization of the synthesis of CF 3 N 3 (1a)w as carried out using the strategy outlined in Scheme 1c.U nlike the reactions of silane 2a with carbonyl compounds,w here ac atalytic amount of initiator is sufficient (the catalytic cycle is maintained by the intermediate alkoxide), in our case, an equimolar amount of the initiator was necessary.A nhydrous fluoride-or oxygen-containing initiators were explored and the reaction was monitored by 19 FNMR to determine yields of 1a and the side products fluoroform (4)a nd difluorosilicate 5 (Table 1). With K 2 CO 3 in DMF,s ilane 2a was converted slowly at ambient temperature or within one (6), and significant amounts of difluorosilicates 5 ( Table 1, entries 1-3).…”