[Hydroxy(tosyloxy)iodo]benzene (HTIB)

Abstract

(A) A facile, general and high-yielding protocol for the synthesis of novel α-tosyloxy β-keto sulfones is described utilizing the relatively non-toxic HTIB under solvent-free conditions at room temperature.2 (Chemical Equation Presented) (B) Reaction of various ketones with HTIB followed by treatment of the α-tosyloxy ketones thus generated in situ with sodium azide, possibly in the presence of a phase-transfer catalyst, at room temperature offers a one-pot procedure for the synthesis of α-azido ketones.3,4 (Chemical Equation Presented) (C) Ketones react with HTIB in DMSO-H2O to afford α-hydroxy ketones under neutral conditions and in good yields.5 (Chemical Equation Presented) (D) Spirodienones bearing a 1-azaspiro[4.5]decane ring have been synthesized from N-methoxy-(4-halogenophenyl)amides by the intramolecular ipso attack of a nitrenium ion generated with HTIB in trifluoroethanol.6 (Chemical Equation Presented) (E) The treatment of aryl alkenes with HTIB in 95% methanol affords the corresponding α-aryl ketones. This oxidative rearrangement is general for acyclic and cyclic aryl alkenes and permits regioselective synthesis of isomeric α-phenyl ketone pairs.7 (Chemical Equation Presented) (F) Polycyclic aromatic hydrocarbons (PAH) undergo regioselective oxidative substitution with HTIB in dichloromethane to give the corresponding aryl sulfonate esters.8 (Chemical Equation Presented) (G) Oxidation of 3-cinnamoyl-4-hydroxy-6-methyl-2H-pyran-2-ones with HTIB in CH 2Cl2 leads to cyclization, thereby providing a new and convenient route for the synthesis of 3-aryl-7-methylpyrano[4,3-b]pyran-4H,5H- diones.9 (Chemical Equation Presented) (H) Oxidation of flavanones to flavones was developed using HTIB in ionic liquid 1,3-di-n-butylimidazolium bromide at room temperature.10 (Chemical Equation Presented) (I) The oxidation of benzylic alcohols with HTIB provides a rapid and convenient method to prepare corresponding carbonyl compounds under solvent-free conditions. 11 (Chemical Equation Presented) (J) A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with HTIB followed by magnesium halides under solvent-free conditions.12 (Chemical Equation Presented). © Georg Thieme Verlag Stuttgart.