Asymmetric Palladium-Catalyzed Alkene Carboamination Reactions for the Synthesis of Cyclic Sulfamides

Article abstract of DOI:10.1002/chem.201600887

The synthesis of cyclic sulfamides by enantioselective Pd-catalyzed alkene carboamination reactions between N-allylsulfamides and aryl or alkenyl bromides is described. High levels of asymmetric induction (up to 95:5 e.r.) are achieved using a catalyst composed of [Pd₂(dba)₃] and (S)-Siphos-PE. Deuterium-labelling studies indicate the reactions proceed through syn-aminopalladation of the alkene and suggest that the control of syn- versus anti-aminopalladation pathways is important for asymmetric induction. Aminate the double bond! The enantioselective Pd-catalyzed coupling of aryl or alkenyl bromides with N-allylsulfamides affords substituted cyclic sulfamides in good yield with high levels of asymmetric induction (see scheme). The reactions proceed through stereoselective syn-aminopalladation of the alkene, which is important for high enantioselectivity.