Chiral arylsulfinylamides: all-in-one reagents for visible light-mediated asymmetric alkene aminoarylations

Abstract

Two- or one-electron mediated alkene aminoarylations represent straightforward approaches to assemble molecular complexity by the simultaneous formation of two contiguous Csp3-Csp2/Csp3-N stereocenters. While racemic versions have been extensively explored, asymmetric variants, especially those involving open-shell C-centered radical species, are much more limited both in number and scope. In this work, we describe enantioenriched arylsulfinylamides as all-in-one reagents for the efficient asymmetric, intermolecular aminoarylation of alkenes. Under mild photoredox conditions, Nitrogen addition of the arylsulfinylamide onto the double bond followed by 1,4-translocation of the aromatic ring produce the corresponding aminoarylation adducts in a single operation. The sulfinyl group acts here as a traceless chiral auxiliary and is eliminated in situ under the reaction conditions. Optically pure beta, beta-diarylethyl- and aryl-alpha, beta-ethylenediamines, prominent motifs in pharmaceuticals and bioactive natural products, are obtained with excellent levels of regio-, relative and absolute stereocontrol.