Organohypervalent Iodine: Development, Applications, and Future Directions

ArticleinThe Journal of Organic Chemistry 70(8):2893-903 · May 2005with12 Reads
DOI: 10.1021/jo050117b · Source: PubMed
The synthetic utility of organohypervalent iodine reagents will be illustrated by their use in the alpha-hydroxydimethylacetal formation reaction from enolizable ketones, alpha-hydroxylation, alpha-tosyloxylation, alpha-alkoxylation and arylation of ketones, carbon-carbon bond formation, and intramolecular cyclopropanation using iodonium ylides. The uses of these reagents in the Hunsdiecker reaction of carboxylic acids and Hofmann rearrangement of carboxamides is presented. Specific transformation in the cubane series are discussed. The syntheses of a wide range of heterocycle structures are also presented. A unifying pathway for virtually all these diverse reactions is offered; the central features being initial attack at the iodonium center, ligand coupling, with reductive elimination of iodobenzene to yield the product.
    • "This is not surprising considering the importance of improving oxidative reactions and reducing their environmental impact. Hypervalent iodine reagents are a great alternative to toxic heavy metals often used to effect similar transformations678910. Among the plethora of iodine(III) compounds [11], it is undeniable that the (diacetoxyiodo)arenes remain the most common and used ones [12]. "
    [Show abstract] [Hide abstract] ABSTRACT: The oxidation of iodoarenes is central to the field of hypervalent iodine chemistry. It was found that the metathetical redox reaction between (diacetoxyiodo)arenes and iodoarenes is possible in the presence of a catalytic amount of Lewis acid. This discovery opens a new strategy to access (diacetoxyiodo)arenes. A computational study is provided to rationalize the results observed.
    Full-text · Article · Dec 2015
    • "Unstable monocarbonyl iodonium ylides have been prepared from 2-acetoxyvinyliodonium salts by Ochiai et al. [4]. In general iodonium ylides have been used as carbene precursors under thermal, photochemical and catalytic conditions23456789. Very recently, we have reported that 1,3-dicarbonyl compounds react with HF or HCl in the presence of iodosylbenzene (PhIO) to give 2-fluoro-or 2-chloro-1,3-dicarbonyl compounds in good to high yields [10,11]. "
    [Show abstract] [Hide abstract] ABSTRACT: Reaction of dibenzoylmethane with (diacetoxyiodo)benzene in the presence of KOH in MeCN quantitatively gave the corresponding iodonium ylide, which was treated with a HF reagent to afford the corresponding 2-fluorinated dibenzoylmethane in 14-50% yields. The similar reaction of the iodonium ylides obtained from 1-phenylbutan-1,3-dione, ethyl benzoylacetate, and ethyl p-nitrobenzoylacetate with TEA·3HF gave the corresponding fluorinated products in 17-34% yields. It is suggested that the fluorinated products were formed through the C-protonation of the ylide, followed by displacement with fluoride ion. The same reaction of the iodonium ylide of dibenzoylmethane with concentrated HCl gave the corresponding chlorinated product in 45% yield.
    Full-text · Article · Dec 2012
    • "In the last quarter of a century, the chemistry of hypervalent iodine has been extensively studied due to the increasing importance of greener synthetic processes123456789. A number of iodine(III) and iodine(V) reagents, e.g., phenyliodine(III) diacetate (PIDA), phenyliodine(III) bis(trifluoroacetate) "
    [Show abstract] [Hide abstract] ABSTRACT: In this manuscript, we report clear evidence for the generation of aromatic cation radicals produced by using [hydroxy(tosyloxy)iodo]benzene (HTIB) in fluoroalcohol solvents such as 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). The single-electron-transfer (SET) oxidation ability of HTIB to give cation radicals was first established by ESR and UV measurements. The reaction was broadly applied to various thiophenes, and unique thienyliodonium salts were directly synthesized by this method in excellent yields without the production of any harmful byproducts.
    Full-text · Article · Mar 2010
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