New Reactions of IBX: Oxidation of Nitrogen- and Sulfur-Containing Substrates To Afford Useful Synthetic Intermediates
K. C. Nicolaou*, Casey J. N. Mathison, Tamsyn Montagnon
*Department of Chemistry and The Skaggs Institute for Chemical Biology, The
Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037,
USA, Email: kcnscripps.edu
K. C. Nicolaou, C. J. N. Mathison, T. Montagnon, Angew. Chem. Int. Ed., 2003, 42, 4077-4082.
DOI: 10.1002/anie.200352076
Abstract
A number of new reactions of IBX with heteroatom-containing substrates were discovered and their utility was demonstrated. IBX was used for the generation of imines from secondary amines in notably high yields, for the oxidative aromatization of nitrogen heterocycles and for the cleavage of dithianes.
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Details
The document discusses the resurgence of interest in o-iodoxybenzoic acid (IBX) as a versatile reagent for organic synthesis, particularly in the oxidation of nitrogen- and sulfur-containing substrates. Initially described in 1893, IBX gained renewed attention in the 1980s due to the work of Dess and Martin. Recent advancements have improved its synthesis and expanded its applications. IBX is effective in oxidizing ketones, aldehydes, silyl enol ethers, and benzylic positions, and in facilitating the cyclization of N-aryl amides, (thio)carbamates, and ureas. The document highlights IBX's ability to oxidize a wide range of amines to imines and oximes under mild conditions with high yields, and its regioselectivity in these transformations. Additionally, IBX can oxidize cyclic amines to aromatic heterocycles and cleave dithianes to carbonyl compounds. The study emphasizes the utility of IBX in organic synthesis, offering mild and efficient methods for generating valuable synthetic intermediates. The research was supported by the National Institutes of Health and the Skaggs Institute for Chemical Biology, with contributions from various researchers and institutions.
Key Words
imines, imidazoles, oxidation, oximes, synthetic methods, IBX, dithianes
ID: J06-Y2003-770