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

作　　者：Yan-Bo Li Yi Li Liang Yin 

机构地区：[1]CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Centre for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Chinese Chemical Letters》2024年第7期264-270,共7页中国化学快报（英文版）

基　　金：the financial support from the National Natural Science Foundation of China(No.22271302);the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417100 and 21XD1424800);CAS Key Laboratory of Synthetic Chemistry of Natural Substances;Shanghai Institute of Organic Chemistry。

摘　　要：A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,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 both1H and31P 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 andα,β-unsaturated thioamides facilitated the nucleophilic addition.Finally,both Michael adducts and(R)-HP(S)PhOMe are easily converted to synthetically useful compounds.

关 键 词：Copper catalysis Asymmetric catalysis Diastereodivergent synthesis P-Chirality "Soft-soft"interaction 

分 类 号：O621.251[理学—有机化学]