o-Iodoxybenzoic acid (IBX) as a viable reagent in the manipulation of nitrogen- and sulfur-containing substrates: scope, generality, and mechanism of IBX-mediated amine oxidations and dithiane deprotections.
o-Iodoxybenzoic acid (IBX), a highly versatile hypervalent iodine(V) reagent, was found to efficiently mediate the dehydrogenation of amines in addition to facilitating the oxidative cleavage of dithioacetals and dithioketals. Through the development of relevant IBX-based protocols, a plethora of useful synthetic intermediates, including imines, oximes, ketones, and aromatic N-heterocycles, were found to be readily accessible under notably mild conditions. Further investigation of these transformations led to the elucidation of valuable mechanistic details, resulting in the conclusion that they proceed via ionic rather than single electron transfer (SET) pathways.
Nicolaou
K C
KC
Department of Chemistry and Skaggs Institute for Chemical Biology, Scripps Research Institute, La Jolla, California 92037, and Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093 USA. kcn@scripps.edu
Mathison
Casey J N
CJ
Montagnon
Tamsyn
T
D000080:Acetals / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry; D006865:Hydrogenation; D007097:Imines / Q000737:chemistry; D007202:Indicators and Reagents; D007462:Iodobenzenes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D008956:Models, Chemical; D009584:Nitrogen / Q000737:chemistry*; D010084:Oxidation-Reduction; D010091:Oximes / Q000737:chemistry; D011807:Quinolizines / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D013457:Sulfur Compounds / Q000737:chemistry*
D000080:Acetals; D000588:Amines; D006571:Heterocyclic Compounds; D007097:Imines; D007202:Indicators and Reagents; D007462:Iodobenzenes; D007659:Ketones; D010091:Oximes; D011807:Quinolizines; D013457:Sulfur Compounds; C438055:dithiane; C476101:o-iodoxybenzoic acid; D013455:Sulfur; D009584:Nitrogen