The synthetic utility of organohypervalent iodine reagents will be illustrated by their use in the α-hydroxydimethylacetal formation reaction from enolizable ketones, α-hydroxylation, α-tosyloxylation, α-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.

Organohypervalent iodine: development, applications, and future directions.

Direct α-hydroxylation of ketones under acidic conditions using [bis (trifluoroacetoxy)] iodobenzene

Enantioselective synthesis of protected α-hydroxy aldehydes and ketones via hydroxylation of metalated chiral hydrazones

Elemental Fluorine and HOF·CH3CN in Service of General Organic Chemistry

Cyclic seleninate esters serve as catalysts for the rapid oxidation of sulfides to sulfoxides, alkenes to epoxides, and enamines to α-hydroxyketones. Optimal conditions were found that minimize the overoxidation of the product sulfoxides to sulfones and the hydrolysis of epoxides to diols. In some examples such as styrene derivatives, oxidative cleavage was observed instead of epoxidation. The enamine oxidations proceed via the initial formation of dimeric 2,5-diamino-1,4-dioxane species, which were hydrolyzed in situ to the final products. The structure of one such dimer was confirmed by X-ray crystallography.

Cyclic seleninate esters as catalysts for the oxidation of sulfides to sulfoxides, epoxidation of alkenes, and conversion of enamines to α-hydroxyketones.

Judy Toczek

Papers

The reaction of chromyl chloride and O-silylated enolates: a novel regiospecific route to α-hydroxy ketones.☆