手性 C(2)对称脯氨酸衍生的β-氨基醇促进的三甲基硅基乙炔对 N-膦酰亚胺的对映选择性亲核加成。

Enantioselective nucleophilic addition of trimethylsilylacetylene to n-phosphinoylimines promoted by C(2)-symmetric proline-derived beta-amino alcohol.

机构信息

Institute of Biochemistry and Molecular Biology and State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.

出版信息

J Org Chem. 2009 Sep 18;74(18):6980-5. doi: 10.1021/jo901492w.

DOI:10.1021/jo901492w

PMID:19694410

Abstract

Both C(2)- and C(3)-symmetric proline-derived beta-amine alcohol ligands were designed, synthesized, and successfully applied to the enantioselective direct addition of trimethylsilylacetylene to N-phosphinoylimines. Aromatic, heteroaromatic, and aliphatic N-(diphenylphosphinoyl) imines and several N-(diethoxyphosphoryl) imines were tested, and optically active propargylic amides in good yields (up to 92%) and excellent enantioselectivities (up to 95%) were obtained by the simple experimental procedure. The convenience, mild conditions, and easy deprotection of the phosphonamide products made the present method very attractive. Furthermore, the Michael-type addition process of C horizontal lineN alkynylation was studied and proposed on the basis of React (31)P NMR investigation.

摘要

两种 C(2)-和 C(3)-对称脯氨酸衍生的β-胺醇配体被设计、合成，并成功应用于三甲基硅基乙炔对 N-膦酰亚胺的对映选择性直接加成。芳香族、杂芳香族和脂肪族 N-(二苯基膦酰基)亚胺以及几种 N-(二乙氧基磷酰基)亚胺都进行了测试，通过简单的实验程序，以良好的收率（高达 92%）和优异的对映选择性（高达 95%）获得了光学活性的炔丙酰胺产物。该方法具有操作简便、条件温和、膦酰胺产物易于脱保护等优点，非常有吸引力。此外，基于 React (31)P NMR 研究，还研究并提出了 C 水平线上 N-炔基化的迈克尔型加成过程。