Abstract
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 diastereo-and enantioselectivities.In this reaction,the kinetic resolution of HP(S)ROR'occurs,which affords(R)-HP(S)PhOMe 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 be-tween the[Cu]-SPROR'species and α,β-unsaturated thioamides facilitated the nucleophilic addition.Fi-nally,both Michael adducts and(R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
基金项目
National Natural Science Foundation of China(22271302)
Science and Technology Commission of Shanghai Municipality(20JC1417100)
Science and Technology Commission of Shanghai Municipality(21XD1424800)
CAS Key Laboratory of Synthetic Chemistry of Natural Substances,and Shanghai Institute of Organic Chemistry()
万方数据