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[Bis(trifluoroacetoxy)iodo]benzene acts as a reagent in Pummerer-like reactions. It plays an important role in the direct alfa-hydroxylation of ketones under acidic conditions. It is involved in the cyclization of styryl amines to N-alkyl or N-aryl indoles. It serves as a reagent for the chemoselective deprotection of dimethoxybenzyl ethers and tosyloxylation of anilides. Further, it is used in the synthesis of 1,3,4-oxadiazoles by the oxidation of N-acylhydrazones. In addition to this, it is employed in the Hofmann rearrangement for the conversion of cyclobutanecarboxamide to cyclobutylamine hydrochloride.
Hypervalent iodine oxidizing agent, cf Iodosobenzene diacetate, B24531. PIFA oxidizes hydroquinones and catechols to benzoquinones. In the presence of a nucleophile, 4-substituted phenols give the corresponding 4,4-disubstituted cyclohexadienone: J. Chem. Soc., Perkin 1, 1891 (1993); 2047 (1994), and refs. therein. In water, 1,4-dimethoxy aromatics undergo oxidative demethylation to p-quinones: Tetrahedron Lett., 42, 6899 (2001). In TFA, acetanilides can be hydroxylated in the p-position: J. Org. Chem., 67, 7424 (2002).
Terminal alkynes are oxidized by PIFA to ɑ-hydroxy ketones: Tetrahedron Lett., 26, 3837 (1985).
Primary amides undergo a Hofmann-like rearrangement to amines, avoiding the harsh conditions often required for the classical method: J. Org. Chem., 49, 4272, 4277 (1984); Synth. Commun., 18, 1615 (1988); Org. Synth. Coll., 8, 132 (1993). Promotes the azidation of alkyl groups of p-alkylanisoles with TMS azide: Tetrahedron Lett., 32, 4321 (1991); J. Am. Chem. Soc., 116, 3684 (1994); Synlett, 427 (1994), and also the direct nucleophilic sulfenylation and thiocyanation of phenol ethers with thiols and TMS isothiocyanate respectively: Synlett, 211 (1995); J. Org. Chem., 60, 7144 (1995).
Mediates the selective cyanation of electron-rich aromatics with Trimethylsilyl cyanide, A19598, e.g. indoles to 2-cyanoindoles: Org. Lett., 7, 537 (2005).
For a brief feature on uses of this reagent in synthesis, see: Synlett, 2851 (2006). For a comprehensive review of polyvalent iodine compounds, see: Chem. Rev., 96, 1123 (1996).
Chatterjee, N.; Bhatt, D.; Goswami, A. A novel transition metal free [bis-(trifluoroacetoxy)iodo]benzene (PIFA) mediated oxidative ipso nitration of organoboronic acids. Org. Biomol. Chem. 2015, 13 (17), 4828-4832.
Chatterjee, N.; Goswami, A. Metal and base free synthesis of primary amines via ipso amination of organoboronic acids mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA). Org. Biomol. Chem. 2015, 13 (29), 7940-7945.
Hazard Statements: H315-H319-H335
Causes skin irritation. Causes serious eye irritation. May cause respiratory irritation.
Precautionary Statements: P261-P280a-P305+P351+P338-P304+P340-P405-P501a
Avoid breathing dust/fume/gas/mist/vapours/spray. Wear protective gloves and eye/face protection. IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. IF INHALED: Remove to fresh air and keep at rest in a position comfortable for breathing. Store locked up. Dispose of contents/container in accordance with local/regional/national/international regulations.