Fluoroalkylation of aromatics: An intramolecular radical cyclization of 4-chloro-1,1,2,2,3,3,4,4-octafluorobutylbenzenes

Copper Causes Regiospecific Formation of C4F8‐Containing Six‐Membered Rings and their Defluorination/Aromatization to C4F4‐Containing Rings in Triphenylene/1,4‐C4F8I2 Reactions

“…[12] However,n one of these reactions were regioselective, let alone regiospecific,i nt he same way as in our reactions, because formation of the six-membered rings could only produce one isomer per aromatic ring (i.e., each aromatic ring in each substrate had only two CÀHb onds available for substitution). In addition, Vicic and co-workersh ave reported as eries of arene(C 4 2À (the latter complexi samodel for ap ossible Cu-surface species Cu(s)-CF 2 CF 2 CF 2 CF 2 -Cu(s)t hat could react in ac oncertedf ashion with surface-bound TRPH in our reactions).…”

“…Concerning the selectiveR D/A of aliphatic C 4 F 8 to aromatic C 4 F 4 groups to increase the number of conjugatedC (sp 2 ) 6 rings in an aromatic precursor,t he most closely relatede xamples in the literature include the treatment of Zn(TPP(C 4 F 8 )) with Na 2 S 2 O 4 /NaHCO 3 in DMSO/CH 2 Cl 2 to form Zn(TPP (C 4 F 4 )), [12] but these reactions did not involve Cu, or any other metal, as the RD/A agent. Therefore, the clean conversion of 2,3-C 4 F 8 to 2,3-C 4 F 4 demonstrates for the first time that hot Cu metal promotess elective defluorination and should be added to the list of reagents [6] available to the synthetic chemistf or CÀFa ctivation.…”

Perfluoroalkylation reactions of (hetero)arenes

“…44 The substrates for the intramolecular cyclization reaction are synthetized using two different methodologies: (i) reaction of arenes with 1-chloro-4-iodooctauorobutane in the presence of Na 2 S 2 O 4 in DMSO and, (ii) copper-catalyzed cross-coupling reaction of aryl iodides with 1-chloro-4-iodooctauorobutane and, in all cases, the substrates were obtained in good yields (Scheme 17). 44 The substrates for the intramolecular cyclization reaction are synthetized using two different methodologies: (i) reaction of arenes with 1-chloro-4-iodooctauorobutane in the presence of Na 2 S 2 O 4 in DMSO and, (ii) copper-catalyzed cross-coupling reaction of aryl iodides with 1-chloro-4-iodooctauorobutane and, in all cases, the substrates were obtained in good yields (Scheme 17).…”

“…Chen and co-workers have reported an interesting intramolecular peruoroalkylation reaction of chloroper-uoroalkylarenes with Na 2 S 2 O 4 in DMSO at room temperature in moderate to good yields. 44 The substrates for the intramolecular cyclization reaction are synthetized using two different methodologies: (i) reaction of arenes with 1-chloro-4-iodooctauorobutane in the presence of Na 2 S 2 O 4 in DMSO and, (ii) copper-catalyzed cross-coupling reaction of aryl iodides with 1-chloro-4-iodooctauorobutane and, in all cases, the substrates were obtained in good yields (Scheme 17). The intramolecular radical cyclizations are carried out under sulnatodehalogenation conditions by using Na 2 S 2 O 4 in DMSO at room temperature and the peruoroalkyl cyclic products are obtained in high yields as sole products with complete conversion of the starting material (Scheme 17).…”

An Efficient Method for the Preparation of Pentafluoroiodoethane from Chloropentafluoroethane

“…Perfluoroalkyl chlorides were found to be converted to the corresponding iodides by this method. [20][21][22] In view of the importance of pentafluoroiodoethane in fluorochemical industry and the necessity of removing CF 3 CF 2 Cl, we investigated the conversion from CF 3 CF 2 Cl to CF 3 CF 2 I and found that the modified sulfinatodehalogenation reaction can also be used in the synthesis of telogen (CF 3 CF 2 I) for R f I from the byproduct (CF 3 CF 2 Cl). Herein we report the results.…”