Thiols, aryl with Grignard reagents

These 0x0 Re complexes can furnish various derivatives, for example, with N-, 0-, S-, or C- ligands, that is, Re oxo-amido, -imido, -alkoxide, -phenoxide, -diolate, -thiolate, -alkyl, or - aryl complexes, on reactions of (13) or (14) with amines, alcohols, phenoxides, diols, thiols, organozinc, or Grignard reagents, respectively. 

Aryl-A3-iodanes bearing an electron-deficient alkyl ligand such as aryl(sul-fonylmethyl)-A3-iodanes (Section 3.2.7) and aryl(perfluoroalkyl)-A3-iodanes are relatively stable. A series of (perfluoroalkyl)phenyl-A3-iodanes 96 were synthesized in good yields by treating bis(trifluoroacetoxy)-A3-iodanes with benzene in the presence of triflic acid [47]. The AModanes 96 transfer the perfluoroalkyl groups to a variety of nucleophiles with reductive elimination of iodobenzene. The nucleophiles involve Grignard reagents, alkyllithiums, enolate anions, alkenes, alkynes, trimethylsilyl enol ethers, arenes, phenols, and thiols. In these reactions, the AModane 96 serves as a source of the perfluoroalkyl cation and, in... 

Sulfides, or thioethers, are sulfur analogues of ethers, and like ethers they can be either symmetrical (R2S) or unsymmetrical (RSR1, where R and R are different). Sulfides can be prepared from alkyl halides by a Williamson-type synthesis with sodium hydrogen sulfide, sodium thiolate or sodium sulfide from alkyl or aryl halides via the Grignard reagent (11) from alkenes by radical-catalysed addition of thiols or by reduction of sulfoxides (Scheme 9).2b... 

Preparation of thiol esters of highly elaborated phosphoranes with thiopyridyl chloroformate has been reported. Treatment of the thiol ester with an aryl Grignard reagent gives the corresponding ketone without epimerization of the chiral centers (eq 7). ... 

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