Versatile and iodine atom-economic co-iodination of alkenes.

Molecular iodine, I(2), is readily converted into 2 equiv of acetyl hypoiodite (CH(3)CO(2)I) via oxidation by (diacetoxyiodo)benzene (DAIB) followed by trapping of the iodide ion by acetoxyphenyl iodonium ion formed. The in situ generated CH(3)CO(2)I is utilized for the synthesis of 1,2-iodo-cofunctionalized derivatives of a variety of alkenes. Conversion of both iodine atoms of I(2) to I(+) sources results in 100% iodine atom economy for the reported iodo-cofunctionalization of alkenes.

Oxidative cleavage of alkenes using an in situ generated iodonium ion with oxone as a terminal oxidant.

A facile and operationally convenient catalytic procedure for oxidative cleavage of alkenes is described. In situ formed [hydroxy(4-carboxyphenyl)iodonium]ion, 2, from the oxidation of 4-iodobenzoic acid, 1, has been shown to facilitate the cleavage of a variety of alkenes in presence of Oxone as a co-oxidant. Optimization of the reaction conditions using 1-phenyl-1-cyclohexene, 3, and the competitive oxidative cleavage of different substrates using the optimized conditions has uncovered important mechanistic details of the reaction.

In situ generation of o-iodoxybenzoic acid (IBX) and the catalytic use of it in oxidation reactions in the presence of Oxone as a co-oxidant.

[structure: see text] Catalytic use of o-iodoxybenzoic acid (IBX) in the presence of Oxone as a co-oxidant is demonstrated for the oxidation of primary and secondary alcohols in user- and eco-friendly solvent mixtures. Also demonstrated is the in situ (re)oxidation of 2-iodosobenzoic acid (IBA) and even commercially available 2-iodobenzoic acid (2IBAcid) by Oxone to IBX allowing one to use these less hazardous reagents, in place of potentially explosive IBX, as catalytic oxidants.