An Asymmetric Redox Arylation: Chirality Transfer from Sulfur to Carbon through a Sulfonium [3,3]‐Sigmatropic Rearrangement

A general, asymmetric redox arylation of ynamides and thioalkynes with chiral sulfoxides is reported. This is the first example of a general 1,4‐chirality transfer from sulfur to a carbon stereocenter through a sulfonium 3,3]‐sigmatropic rearrangement. This reaction delivers α‐arylated thioesters and amides under mild conditions in an atom‐economical manner. The products are formed in high yields with enantiomeric ratios up to 99.5:0.5. Quantum chemical calculations suggest a mechanism for the chirality transfer from sulfur to carbon and explain the experimentally observed correlation of the enantioselectivity with both the catalyst and the substrate.