Copper(Ⅰ)-catalyzed diastereodivergent construction of vicinal P-chiral and C-chiral centers facilitated by dual “soft-soft” interaction

A copper（Ⅰ）-catalyzed diastereodivergent addition of phosphinothioates(HP（S）ROR') to α,β-unsaturated thioamides is disclosed, which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand enantioselectivities. In this reaction, the kinetic resolution of HP（S）ROR' occurs, which affords（R）-HP（S）Ph OMe in high enantioselectivity in the addition with（R,R）-Ph-BPE as the ligand. It is found through control experiment that dual “soft-soft” interaction, indicated by both 1H and 31P NMR experiments,is indispensable in the present reaction. The first “soft-soft” interaction between copper（Ⅰ） catalyst and HP（S）ROR' enables facile deprotonation to generate nucleophilic [Cu]-SPROR' species. The second one between the [Cu]-SPROR' species and α,β-unsaturated thioamides facilitated the nucleophilic addition. Finally, both Michael adducts and（R）-HP（S）PhOMe are easily converted to synthetically useful compounds.