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立体动态催化剂中的超分子手性转移

Supramolecular chirality transfer in a stereodynamic catalysts.

作者信息

Storch Golo, Trapp Oliver

机构信息

Department Chemie, Ludwig-Maximilians-Universität München, Munich, Germany.

Max-Planck-Institute for Astronomy, Heidelberg, Germany.

出版信息

Chirality. 2018 Oct;30(10):1150-1160. doi: 10.1002/chir.23007. Epub 2018 Aug 13.

DOI:10.1002/chir.23007
PMID:30103282
Abstract

We present rhodium catalysts that contain stereodynamic axially chiral biphenol-derived phosphinite ligands modified with non-stereoselective amides for non-covalent interactions. A chirality transfer was achieved with (R)- or (S)-acetylphenylalanine methyl amide, and the interaction mechanism was investigated by NMR measurements. These interactions at the non-stereoselective interaction sites and the formation of supramolecular complexes result in an enrichment of either the (R )- or (S ) enantiomer of the tropos catalysts, which in turn provide the (R)- or (S)-acetylphenylalanine methyl ester in the hydrogenation of (Z)-methyl-α-acetamidocinnamate.

摘要

我们展示了含有经非立体选择性酰胺修饰的用于非共价相互作用的立体动力学轴向手性联苯酚衍生亚膦酸酯配体的铑催化剂。通过(R)-或(S)-乙酰基苯丙氨酸甲酯实现了手性转移,并通过核磁共振测量研究了相互作用机制。这些在非立体选择性相互作用位点的相互作用以及超分子配合物的形成导致了对流催化剂的(R)-或(S)对映体的富集,这反过来又在(Z)-甲基-α-乙酰氨基肉桂酸甲酯的氢化反应中提供了(R)-或(S)-乙酰基苯丙氨酸甲酯。

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Supramolecular chirality transfer in a stereodynamic catalysts.立体动态催化剂中的超分子手性转移
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