Ruthenium-Catalyzed Reactions for Organic Synthesis.

Catalytic amounts of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) are used in combination with [bis(acetoxy)iodo]benzene (BAIB) as a stoichiometric oxidant in the conversion of primary and secondary alcohols to carbonyl compounds. This procedure works efficiently at room temperature in almost all common solvents and neat in some cases. This process exhibits a very high degree of selectivity for the oxidation of primary alcohols to aldehydes, without any noticeable overoxidation to carboxyl compounds, and a high chemoselectivity in the presence of either secondary alcohols or of other oxidizable moieties. This procedure allows an easy, convenient, high-yielding method for the oxidation of alcohols starting from commercially available compounds.

A Versatile and Highly Selective Hypervalent Iodine (III)/2,2,6,6-Tetramethyl-1-piperidinyloxyl-Mediated Oxidation of Alcohols to Carbonyl Compounds

Synthesis of sulfoxides by oxidation of thioethers

Chemical transformations induced by hypervalent iodine reagents

Oxidation of sulfides to sulfoxides. Part 1: Oxidation using halogen derivatives

Catalyzed oxidation of alcohols and aldehydes with iodosylbenzene

Disubstituted acetylenes are oxidized with PhIO in presence of Ru-catalysts to afford α-diketones in 65–85% yield. Under the same conditions terminal acetylenes are cleaved to carboxylic acids.

Ru-Catalyzed Oxidation of Acetylenes to α-Diketones with Iodosylbenzene

Ru-catalyzed oxidation of substituted acetylenes to α-keto esters and α-keto amides with iodosylbenzene

Oxidation of sulfides with PhIO/RuCl2 (PPh3)3 leads to sulfones. Electronwithdrawing substituents in the aromatic ring of PhIO reduce the reactivity and improves selectivity of the system. Thus, with m-iodosylbenzoic acid sulfides are converted to sulfoxide. Under the same conditions aliphatic primary alcohols are transformed to aldehydes with m-iodosylbenzoic acid, while PhIO affords carboxylic acids.

José Godoy

Papers

Catalyzed oxidation of alcohols and aldehydes with iodosylbenzene

Ru-Catalyzed Oxidation of Acetylenes to α-Diketones with Iodosylbenzene

Ru-catalyzed oxidation of substituted acetylenes to α-keto esters and α-keto amides with iodosylbenzene

Ru-Catalyzed Oxidations with Iodosylbenzene Derivatives. Substituent Effects on Selectivity in Oxidation of Sulfides and Alcohols