Iodine(V) reagents in organic synthesis. Part 4. o-Iodoxybenzoic acid as a chemospecific tool for single electron transfer-based oxidation processes.
o-Iodoxybenzoic acid (IBX), a readily available hypervalent iodine(V) reagent, was found to be highly effective in carrying out oxidations adjacent to carbonyl functionalities (to form alpha,beta-unsaturated carbonyl compounds) and at benzylic and related carbon centers (to form conjugated aromatic carbonyl systems). Mechanistic investigations led to the conclusion that these new reactions are initiated by single electron transfer (SET) from the substrate to IBX to form a radical cation which reacts further to give the final products. Fine-tuning of the reaction conditions allowed remarkably selective transformations within multifunctional substrates, elevating the status of this reagent to that of a highly useful and chemoselective oxidant.
Nicolaou
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Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Montagnon
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T
Baran
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Zhong
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D006571:Heterocyclic Compounds / Q000138:chemical synthesis*; D006865:Hydrogenation; D007462:Iodobenzenes; D007463:Iodobenzoates / Q000737:chemistry*; D010084:Oxidation-Reduction
D006571:Heterocyclic Compounds; D007462:Iodobenzenes; D007463:Iodobenzoates; C476101:o-iodoxybenzoic acid