Enantioselective nucleophilic addition of trimethylsilylacetylene to n-phosphinoylimines promoted by C(2)-symmetric proline-derived beta-amino alcohol.
Enantioselective nucleophilic addition of trimethylsilylacetylene to n-phosphinoylimines promoted by C(2)-symmetric proline-derived beta-amino alcohol.
复制标题
DOI：
10.1021/jo901492w
复制
发表时间：
2009-08
期刊：
影响因子：
--
通讯作者：
Shaoqun Zhu;Wenjin Yan;B. Mao;Xianxing Jiang;Rui Wang
中科院分区：
文献类型：
--
作者：
Shaoqun Zhu;Wenjin Yan;B. Mao;Xianxing Jiang;Rui Wang
设计、合成了C(2)-和C(3)-对称脯氨酸衍生的β-胺醇配体，并成功应用于三甲基甲硅烷基乙炔对映选择性直接加成到N-膦酰亚胺上。对芳香族、杂芳香族和脂肪族N-(二苯基膦酰基)亚胺和几种N-(二乙氧基磷酰基)亚胺进行了测试，通过简单的实验步骤获得了良好收率（高达92%）和优异对映选择性（高达95%）的光学活性炔丙基酰胺。磷酰胺产物的方便性、条件温和且易于脱保护使该方法非常有吸引力。此外，在React(31)P NMR研究的基础上，研究并提出了C水平线N炔基化的Michael型加成过程。
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.