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Herein we describe the dearomatization of aryl iodanes through an unprecedented "rearrangement/addition" sequence. The process consists of two stages. First, a rapid [3,3] sigmatropic rearrangement of the aryl iodane with an α‐stannyl nitrile affords a highly electrophilic dearomatized intermediate at −78 °C. A low‐temperature rearrangement then enables the unstable dearomatized species to be trapped in situ with various nucleophiles. As a consequence, the reaction not only breaks the aromaticity of the aryl iodane but also sequentially installs two different functional groups, thus resulting in a polysubstituted alicyclic product. [ABSTRACT FROM AUTHOR]

Herein we describe the dearomatization of aryl iodanes through an unprecedented "rearrangement/addition" sequence. The process consists of two stages. First, a rapid [3,3] sigmatropic rearrangement of the aryl iodane with an α‐stannyl nitrile affords a highly electrophilic dearomatized intermediate at −78 °C. A low‐temperature rearrangement then enables the unstable dearomatized species to be trapped in situ with various nucleophiles. As a consequence, the reaction not only breaks the aromaticity of the aryl iodane but also sequentially installs two different functional groups, thus resulting in a polysubstituted alicyclic product. [ABSTRACT FROM AUTHOR]

A three-component reaction between benzyne, oxazolines and chloroform was developed for the synthesis of trichloromethylated chiral oxazolidines. Benzyne not only serves as an electrophile towards oxazolines but also acts as a base for the deprotonation of chloroform. The dual functions of benzyne enable the trichloromethylation of chiral oxazolines and thus construct chiral N,O-quaternary stereocenters. [ABSTRACT FROM AUTHOR]