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钯催化乙烯基碳酸乙烯酯与迈克尔受体的不对称脱羧环加成反应:相邻季立体中心的构建。

Palladium-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with Michael acceptors: construction of vicinal quaternary stereocenters.

机构信息

School of Chemistry and Chemical Engineering, and Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P. R. China).

出版信息

Angew Chem Int Ed Engl. 2014 Oct 13;53(42):11257-60. doi: 10.1002/anie.201407013. Epub 2014 Aug 28.

DOI:10.1002/anie.201407013
PMID:25168969
Abstract

An efficient method for the diastereo- and enantioselective construction of vicinal all-carbon quaternary stereocenters through palladium-catalyzed decarboxylative cycloaddition of vinylethylene carbonates with activated Michael acceptors was developed. By using a palladium complex generated in situ from [Pd2(dab)3]⋅CHCl3 and a phosphoramidite ligand as a catalyst under mild reaction conditions, the process provides multifunctionalized tetrahydrofurans bearing vicinal all-carbon quaternary stereocenters in high yields with a high level of absolute and relative stereocontrol.

摘要

发展了一种通过钯催化乙烯基碳酸乙烯酯与活化的迈克尔受体的脱羧环加成反应来高效构建非对映和对映选择性的毗邻全碳季碳中心的方法。通过使用原位生成的[Pd2(dab)3]⋅CHCl3 和磷酰胺配体的钯配合物作为催化剂,在温和的反应条件下,该过程以高产率提供了带有毗邻全碳季碳中心的多功能四氢呋喃,具有高水平的绝对和相对立体控制。

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