Sulfide alkyl aryl arene

Fluoroalkyl(aryl)iodonium salts are the most stable and practically important class of alkyl(aryl)iodonium derivatives. The application of such salts as electrophilic fiuoroalkylating reagents was reviewed in 1996 by Umemoto [1017]. Perfluoroalkyl(phenyl)iodonium trifiates (FITS reagents) 764 are efficient perfluoroalky-lating reagents toward various nucleophiUe substrates, sueh as arenes, carbanions, alkynes, alkenes, carbonyl compounds, amines, phosphines and sulfides [1017]. Scheme 3.300 shows several representative examples of electrophilic perfluoroalkylations using FITS reagents. 

Different nucleophiles such as methanol, allylsilanes, silyl enol ethers, trimethylsilyl-cyanide, and arenes can be used in this process [62]. When the sulfide itself contains an unsaturated or aromatic fragment and the process is carried out in the absence of a nucleophile, an intramolecular anodic sub-stitution/cyclization might occur [61-63]. Methyl esters of 2-benzothiazolyl-2-alkyl or aryl-acetic acid, oxidized in MeOH/Et4 NCIO4 or H2SO4 in the presence of CUCI2, form 2,2-dimethoxy products (Eq. 7) [64]. 

Much of the research on the SbCls-catalyzed halogenation of arenes has focused on the chlorination and bromination of perfluoroalkyl-substituted aromatics [14]. The reaction of organic disulfides with electron-rich aromatic compounds under catalysis with SbCls and AgSbFg affords unsymmetrical aryl sulfides in modest yields [15a]. Electrophilic sulfinylation and sulfonation can be similarly effected by SbCls [15a-c]. Alkyl- and halobenzenes give thiocyano derivatives when treated with a mixture of SbCls and Pb(SCN)2 in CCI4 [16],... 

The reaction of trifluoromethyl iodide with arene thiolates provides trifluoromethyl aryl sulfides via a single electron transfer (SET) reaction rather than the SN2 reaction, which is the only formal mechanism (Scheme 2.31). In general, perfluoroalkyl (Rf—X), ferf-alkyl, and vinyl and aromatic halides are strongly deactivated for the replacement of halogens with... 

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