使用亚磷酸酯硫代糖苷的不对称烯酰胺氢化反应：以D-糖为催化剂前体合成D-和L-氨基酸酯。

Asymmetric enamide hydrogenation using phosphinite thioglycosides: synthesis of D- and L-aminoesters using D-sugars as catalyst precursors.

作者信息

Khiar Noureddine, Navas Raquel, Suárez Belén, Alvarez Eleuterio, Fernández Inmaculada

机构信息

Instituto de Investigaciones Químicas, C.S.I.C-Universidad de Sevilla, c/. Américo Vespucio, 49, Isla de la Cartuja, 41092 Sevilla, Spain.

出版信息

Org Lett. 2008 Sep 4;10(17):3697-700. doi: 10.1021/ol801301x. Epub 2008 Jul 29.

DOI:10.1021/ol801301x

PMID:18662004

Abstract

Diastereomerically pure cationic Rh(I) complexes derived from phosphinite thioglycosides I were used as catalysts in highly enantioselective hydrogenations of enamides. The conformational similarity of alpha-D-arabinopyranose with beta-L-galactopyranose allows the synthesis of both enantiomers of alpha-amino acid derivatives such as D- and L-DOPA in excellent ee (97% and 98%), using derivatives of the former sugar as catalyst precursors.

摘要

源自亚膦酸酯硫代糖苷I的非对映体纯阳离子Rh(I)配合物被用作烯酰胺高度对映选择性氢化反应的催化剂。α-D-阿拉伯吡喃糖与β-L-吡喃半乳糖的构象相似性使得以前者糖的衍生物作为催化剂前体，能够以优异的对映体过量值（ee值分别为97%和98%）合成α-氨基酸衍生物（如D-和L-多巴）的两种对映体。