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用于非官能化 1,1-二取代烯烃的对映选择性 Rh 催化反马氏加成的杂化膦配体的设计与应用。

Design and Application of Hybrid Phosphorus Ligands for Enantioselective Rh-Catalyzed Anti-Markovnikov Hydroformylation of Unfunctionalized 1,1-Disubstituted Alkenes.

机构信息

Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences , Wuhan University , Wuhan , Hubei 430072 , China.

Department of Chemistry , Southern University of Science and Technology , Shenzhen , Guangdong 518055 , China.

出版信息

J Am Chem Soc. 2018 Apr 18;140(15):4977-4981. doi: 10.1021/jacs.8b00275. Epub 2018 Apr 4.

Abstract

A series of novel hybrid phosphorus ligands were designed and applied to the Rh-catalyzed enantioselective anti-Markovnikov hydroformylation of unfunctionalized 1,1-disubstituted alkenes. By employing the new catalyst, linear aldehydes with β-chirality can be prepared with high yields and enantioselectivities under mild conditions. Furthermore, catalyst loading as low as 0.05 mol % furnished the desired product in good yield and undiminished selectivity, demonstrating the efficiency of this transformation in large-scale synthesis.

摘要

一系列新型杂化磷配体被设计并应用于 Rh 催化的非官能化 1,1-二取代烯烃的对映选择性反马氏加成反应。通过使用新型催化剂,在温和条件下可以高收率和对映选择性地制备具有β手性的直链醛。此外,在 0.05 mol%的低催化剂负载量下,即可得到所需产物,产率和选择性均未降低,这表明该转化在大规模合成中具有高效性。

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