Search

Pseudocyclic arylbenziodoxaboroles are unique aryne precursors under neutral aqueous conditions that selectively react with organic sulfides, forming the corresponding sulfonium salts. This reaction is compatible with various substituents (alkyl, halogen, CN, NO 2 , CHO, and cyclopropyl) in the aromatic ring or alkyl group of the sulfide. Similar reactions of sulfoxides afford o -hydroxy-substituted sulfonium salts. The structures of key products were confirmed by X-ray analysis.

The iodine(III) catalyst, in situ generated from iodoarene as a precatalyst with m-CPBA and Tf 2 NH, promoted the metal-free [2 + 2 + 1] cycloaddition-type reactions of alkynes, nitriles, and oxygen atoms for the regioselective formations of 2,4-disubstituted and 2,4,5-trisubstituted oxazole. A first example of iodine catalysis for multicomponent reactions is represented.

Tetra-n-butylammonium iodide can efficiently catalyze direct azidation of aldehyde C-H bonds with thermally stable azidobenziodoxolone at room temperature. Compared to conventional methods, which require excessive amounts of highly explosive azide sources, this is a safe and convenient procedure.

Hypervalent iodine catalyzed oxidation of aldoximes using oxone as a terminal oxidant generates nitrile oxides, which react with alkenes and alkynes to give the corresponding isoxazolines and isoxazoles in moderate to good yields. This reaction involves active hypervalent iodine species formed in situ from catalytic iodoarene and oxone in the presence of hexafluoroisopropanol in aqueous methanol solution.

The preparation, X-ray structure, and reactivity of new, highly soluble, and reactive iodonium ylides derived from malonate methyl ester and bearing an ortho substituent on the phenyl ring are reported. These new reagents show higher reactivity than common phenyliodonium ylides in the Rh-catalyzed cyclopropanation, C-H insertion, and transylidation reactions under homogeneous conditions.

Alkylcarboxamides can be converted to the respective amines by Hofmann rearrangement using hypervalent iodine species generated in situ from PhI and Oxone in aqueous acetonitrile. On the basis of this reaction, a convenient experimental procedure for the preparation of alkylcarbamates using Oxone as the oxidant in the presence of iodobenzene in methanol has been developed. An efficient method for direct conversion of substituted benzamides to the respective quinone derivatives by treatment with Oxone and iodobenzene in aqueous acetonitrile has also been found.

A simple three-step preparation of polymer-supported N-(2-iodyl-phenyl)-acylamide (NIPA resin) starting from 2-iodoaniline is described. The resin was obtained with good loading levels (0.7-0.8 mmol g(-1)) and has been successfully used for efficient oxidation of a diverse collection of alcohols. Thus, treating alcohols with 1.0 equiv of the resin in 1,2-dichloroethane under reflux for 30-60 min allowed rapid and in most cases complete conversion to the corresponding carbonyl compound.

[reaction: see text] New amino acid-derived iodobenzene dicarboxylates were prepared by the reaction of (diacetoxyiodo)benzene with N-protected natural amino acids. These compounds in the presence of iodide anion can be used as reagents for beta-iodocarboxylation of alkenes leading to the respective amino acid esters.

New N-functionalized benziodazoles were prepared by the peracetic oxidation of 2-iodobenzamides derived from alanine or valine. X-ray crystal structural analysis of two benziodazole-based phenyliodonium derivatives provides insight into facile interchange between benziodazoles and iminium benziodoxoles under acidic or basic conditions. [reaction: see text]