New Perspectives for Iodine (III) Reagents in (Hetero)Biaryl Coupling Reactions

Chemistry of Polyvalent Iodine

“…Numerous reviews on specific classes of polyvalent iodine compounds and their synthetic applications have recently been published 18–61. Most notable are the specialized reviews on [hydroxy(tosyloxy)iodo]benzene,41 the chemistry and synthetic applications of iodonium salts,29,36,38,42,43,46,47,54,55 the chemistry of iodonium ylides,56–58 the chemistry of iminoiodanes,28 hypervalent iodine fluorides,27 electrophilic perfluoroalkylations,44 perfluoroorgano hypervalent iodine compounds,61 the chemistry of benziodoxoles,24,45 polymer-supported hypervalent iodine reagents,30 hypervalent iodine-mediated ring contraction reactions,21 application of hypervalent iodine in the synthesis of heterocycles,25,40 application of hypervalent iodine in the oxidation of phenolic compounds,32,34,50–53,60 oxidation of carbonyl compounds with organohypervalent iodine reagents,37 application of hypervalent iodine in (hetero)biaryl coupling reactions,31 phosphorolytic reactivity of o -iodosylcarboxylates,33 coordination of hypervalent iodine,19 transition metal catalyzed reactions of hypervalent iodine compounds,18 radical reactions of hypervalent iodine,35,39 stereoselective reactions of hypervalent iodine electrophiles,48 catalytic applications of organoiodine compounds,20,49 and synthetic applications of pentavalent iodine reagents 22,23,26,59…”

Atom-economical group-transfer reactions with hypervalent iodine compounds

“…From a synthetic point of view, (dicarboxyiodo)benzenes 20 are probably one of the most popular hypervalent iodine compounds in organic synthesis [ 3 , 9 , 38 – 41 ]. They have been widely applied in C–H oxygenations, nitrene generations, oxidative dearomatisations and dehydrogenative couplings by transferring one of their two carboxyl ligands or external oxygen nucleophiles to a substrate.…”

Development and Application of New Oxidation Systems Utilizing Oxometalate Catalysts

“…The hypervalent iodine(III) reagent, PIFA, induced biaryl coupling reaction involving aromatic cation-radical intermediates was originally developed by our group 89,94,95,97) and applied to the synthesis of some useful heterocycles by Moreno et al 109) The commonly used conditions for biaryl coupling reactions using PIFA are as follows: (i) in poorly nucleophilic solvents such as TFE or HFIP; and (ii) in the presence of BF 3 ·Et 2 O (2 eq) in CH 2 Cl 2 .…”