Hernández-Toribio Jorge, Gómez Arrayás Ramón, Carretero Juan C
Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid, Spain.
J Am Chem Soc. 2008 Dec 3;130(48):16150-1. doi: 10.1021/ja807583n.
An efficient catalytic enantioselective direct Mannich reaction of glycinate Schiff bases with aryl imines leading to anticonfigured orthogonally protected alpha,beta-diaminoesters has been realized. Keys to success in this new catalyst system are the use of Fesulphos/Cu(CH3CN)4PF6 (3-5 mol%) as a Lewis acid catalyst and readily available N-(8-quinolyl)sulfonyl-protected aldimines as substrates, affording excellent levels of diastereo- (typically anti/syn > 90:10) and enantiocontrol (typically > or = 90% ee). A remarkable feature of this catalyst system is that it allows the construction of products with a tetrasubstituted carbon stereocenter at C-alpha in a highly diastereo- and enantiocontrolled manner.
实现了甘氨酸酯席夫碱与芳基亚胺的高效催化对映选择性直接曼尼希反应，生成反式构型的正交保护的α,β-二氨基酯。这种新型催化剂体系成功的关键在于使用Fesulphos/Cu(CH3CN)4PF6（3-5 mol%）作为路易斯酸催化剂，并使用易于获得的N-(8-喹啉基)磺酰基保护的醛亚胺作为底物，可实现出色的非对映选择性（通常反式/顺式>90:10）和对映体控制（通常≥90% ee）。该催化剂体系的一个显著特点是，它能够以高度非对映和对映体控制的方式构建在C-α位具有四取代碳立体中心的产物。
