Hypoiodite-catalyzed reactions

The second example of the hypoiodite-catalyzed C-C coupling reaction is represented by the C3-selective formylation of indoles 149 to products 150 by using A-methylaniline as a formylating reagent in the presence of catalytic B114NI and tert-butyl peroxybenzoate as the terminal oxidant (Scheme 4.76) [118]. Pivalic acid is... 

The homolysis of tertiary hypochlorites for the production of oxy radicals is well known." The ease with which secondary hypohalites decompose to ketones has hampered the application of hypohalites for transannular reactions. However the tendency for the base-catalyzed heterolytic decomposition decreases as one passes from hypochlorites to hypobromites tohypoidites. Therefore the suitability of hypohalites for functionalization at the angular positions in steroids should increase in the same order. Since hypoidites (or iodine) do not react readily with ketones or carbon-carbon double bonds under neutral conditions hypoiodite reactions are more generally applicable than hypochlorite or hypobromite decompositions. 

Another important example of catalytic oxidation of inorganic compounds by peroxidases is the catalysis of iodide oxidation by TPO. TPO is involved in the biosynthesis of thyroid hormone and catalyzes the reactions of iodination and coupling in the thyroid gland. Magnusson et al. [215] considered two possible pathways of iodination the formation of enzyme-bound hypoiodite and the formation of free hypoiodide (Reactions (17) and (18)) ... 

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