N,N-Disubstituted Allylic Amine Type Aminophosphines with C(aryl)-N(amine) Bond Axial Chirality: Synthesis and Application to Palladium-Catalyzed Asymmetric Allylic Alkylation with Malonates.

N,具有 C （ 芳基 ） - N （ 胺 ） 键轴向手性的 N - 二取代烯丙基胺型氨基膦 ： 合成及其在钯催化的不对称烯丙基与丙二酸酯烷基化中的应用。

• 影响指数: 1.628
• 发表时间: Oct 2018 11
• 来源期刊: J Oleo Sci
• DOI: 10.5650/jos.ess17260
• PMID: 30210075
• 文章类型: Journal Article
• 中科院分区: Q3;Q3
• 作者列表: Mino T,Youda J,Ebisawa T,Shima Y,Nishikawa K,Yoshida Y,Sakamoto M

关键词: asymmetric allylic alkylation; axial chirality; palladium; phosphine-olefin type chiral ligand

Mesh: Alkylation; Catalysis; Chromatography, High Pressure Liquid; Malonates / chemistry; Organophosphorus Compounds / chemical synthesis; Palladium / chemistry; Stereoisomerism

Abstract

We designed and synthesized a series of N,N-disubstituted allylic amine type aminophosphines 2, 3 and 4, which are derivatives of chiral ligands 1. Aminophosphines 2-4 (except 2a) exist in C(aryl)-N(amine) bond axial chirality by chiral HPLC analysis. Both enantiomeric isomers of 4b were successfully obtained in an enantiomerically pure form. We demonstrated that 1a, 1b, and 4b can be used as effective chiral ligands for the palladium-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with malonates in high enantioselectivities (up to 90% ee).

摘要

我们设计并合成了一系列N，N-二取代的烯丙基胺型氨基膦2、3和4,其为手性配体1的衍生物。通过手性HPLC分析,氨基膦2-4(除了2a)存在于C(芳基)-N(胺)键轴向手性中。4b的两种对映体异构体均以对映体纯的形式成功获得。我们证明了1a，1b,和4b可用作有效的手性配体，用于高对映选择性（高达90％ee）的1,3-二苯基-2-丙烯基乙酸酯与丙二酸酯的钯催化的不对称烯丙基烷基化。