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

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外文摘要：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.

外文关键词：

Copper catalysisAsymmetric catalysisDiastereodivergent synthesisP-Chirality"Soft-soft"interaction

作者：

Yan-Bo Li、Yi Li、Liang Yin

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作者单位：

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

基金：

National Natural Science Foundation of ChinaScience and Technology Commission of Shanghai MunicipalityScience and Technology Commission of Shanghai MunicipalityCAS Key Laboratory of Synthetic Chemistry of Natural Substances,and Shanghai Institute of Organic Chemistry

项目编号：

2227130220JC141710021XD1424800

出版年：

2024

DOI：

10.1016/j.cclet.2023.109294

中国化学快报(英文版)

中国化学会

中国化学快报(英文版)

CSTPCD

影响因子：0.771

ISSN：1001-8417

年,卷(期)：2024.35(7)