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Palladium-catalyzed asymmetric allylic nucleophilic substitution reactions using chiral tert-butanesulfinylphosphine ligands
Authors:Junmin Chen  Feng Lang  Dong Li  Linfeng Cun  Jin Zhu  Jingen Deng  Jian Liao
Affiliation:1. National Engineering Research Center of Chiral Drugs and Key Laboratory of Asymmetric Synthesis and Chirotechnology of Sichuan Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China;2. Graduate School of Chinese Academy of Sciences, Beijing 100049, China;3. College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China
Abstract:The asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate 3 with dimethyl malonate proceeded smoothly in the presence of lithium acetate, BSA (N,O-bis(trimethylsilyl)acetamide), [Pd(η3-C3H5)Cl]2, and chiral tert-butanesulfinylphosphine ligand 2c to give the allylic alkylation product in good yield and high enantiomeric excess (up to 93% ee), while the enantioselectivities of allylic amination of 3 with various amines were moderate (up to 76% ee).
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