The hype about iodine(III): A chiral hypervalent iodine(III) reagent (1) is reported to enantioselectively dearomatize phenols in a highly selective manner (see scheme). This result clearly supports existence of the associative pathway in hypervalent iodine(III)‐induced phenolic oxidations.

A protic solvent, 2,2,2-trifluoroethanol (CF(3)CH(2)OH), was successfully introduced into hypervalent iodine(III)-involved catalytic cycles as an effective solvent, and the first iodoarene-catalyzed intramolecular carbon-nitrogen bond forming reaction was achieved under strong acid-free and mild conditions.

We have found that the use of fluoroalcohol media greatly enhanced the efficiency and scope of the direct dehydrative condensation of arenes and hypervalent iodine(III) compounds; the present clean method has a broad range of applicability as well as unique selectivity in the aromatic substrates, and is highly efficient even in polymer functionalization.

We have succeeded in the first versatile iodoarene-catalyzed C-C bond-forming reactions by development of a new reoxidation system at low temperatures using stoichiometric bis(trifluoroacetyl) peroxide A in 2,2,2-trifluoroethanol (TFE). The catalytic system supplies a wide range of substrates and functional availabilities sufficient to be used in the key synthetic process of producing biologically important Amaryllidaceae alkaloids.

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