Aryne 1,2,3,5-Tetrasubstitution Enabled by 3-Silylaryne and Allyl Sulfoxide via an Aromatic 1,3-Silyl Migration

Although benzyne has been well-known to serve as a synthon that can conveniently prepare various 1,2-difunctionalized benzenes, the sites other than its formal triple bond remain silent in typical benzyne transformations. An unprecedented aryne 1,2,3,5-tetrasubstitution was realized from 3-silylbenzyne and aryl allyl sulfoxide, the mechanistic pathway of which includes a regioselective aryne insertion into the S=O bond, a [3,6]-sigmatropic rearrangement, and a thermal aromatic 1,3-silyl migration cascade.

Automated summary

An unprecedented aryne 1,2,3,5-tetrasubstitution was achieved through a reaction involving 3-silylbenzyne and aryl allyl sulfoxide. The mechanism includes regioselective aryne insertion into the S=O bond, [3,6]-sigmatropic rearrangement, and thermal aromatic 1,3-silyl migration cascade.