Chirality-Match-Directed Radical Truce–Smiles Rearrangement of N -Arylsulfinyl Allylamines for Stereoselective Construction of Acyclic Quaternary Carbon Stereocenters

The trifluoromethyl radical-promoted Truce–Smiles rearrangement of β-substituted N -arylsulfinyl allylamines facilitates the sequential trifluoromethylation-arylation of their unactivated alkene moiety, yielding chiral amines that feature an acyclic quaternary carbon stereocenter at the β-position. During the aryl 1,4-migration from the arylsulfinyl moiety to the tertiary radical carbon atom, which is substituted with two linear alkyl groups, the challenging enantiofacial differentiation is influenced by the stereochemical configurations of both the sulfinyl group and the α-chiral carbon present in the N -sulfinyl allylamine substrates. Optimal stereocontrol is attained through the employment of diastereomers exhibiting matched chirality.