Stereodivergent telomerization of linear functionalized dienes with amines

Despite the importance of divergent synthesis to obtain different isomers for medicinal and material chemistry, divergent stereocontrol over four distinct selectivity factors remains a fundamental challenge. The telomerization reaction is limited to the transformation of simple unfunctionalized 1,3-dienes to circumvent intractable stereoisomeric mixtures. Here we report an orthogonal telomerization platform using linear functionalized 1,3-dienes as the substrates, which simultaneously dictates regio-, geometric, diastereo-, and enantioselectivities. Diverse types of γ-amino esters are prepared from identical, readily available unsaturated esters and amines via synergistic palladium and acid catalysis, with each precisely obtained out of hundreds of potential telomers. Several chiral phosphoramidite ligands have been developed to promote the transformation. This study showcases the potential of multidimensional stereo-manipulation for the industrially valuable telomerization reaction.