Here we describe an asymmetric [3,3]-sigmatropic rearrangement of aryl iodanes that enables the enantioselective α-arylation of chiral 2-oxazolines, thereby producing valuable chiral α-aryl carbonyl compounds. The success of this protocol hinges on the selective assembly of aryl iodanes with 2-oxazolines and the smooth deprotonation of the in situ-generated iodonium–imine species. The nearly neutral and mild conditions of the reaction allow it to tolerate a wide variety of functional groups. Moreover, the remaining iodine atom in the products not only provides a versatile platform for further elaboration of such molecules but also supplies the asymmetric hypervalent iodine chemistry with a new class of chiral scaffolds.

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.

Herein we describe the dearomatization of aryl sulfoxides with difluoroenol silyl ether (DFESE) using a rearrangement/addition protocol.

A three-component reaction between benzyne, oxazolines and chloroform was developed for the synthesis of trichloromethylated chiral oxazolidines.