Graduate School of Pharmaceutical Sciences, the University of Tokyo , 7-3-1 Hongo Bunkyo-ku, Tokyo 113-0033, Japan.
J Am Chem Soc. 2014 Jun 25;136(25):9190-4. doi: 10.1021/ja5039165. Epub 2014 Jun 16.
Regiodivergent parallel kinetic resolution of aziridines with malonates was achieved under dinuclear Schiff base catalysis. The regiodivergent reaction proceeded under catalyst-control irrespective of the substituents on the aziridines, and 2.5-10 mol % of a Y(OTf)3/La(OiPr)3/a dinucleating Schiff base = 1:1:1 mixture gave versatile γ-amino acid derivatives in 96 → >99.5% ee. Not only terminal but also internal racemic aziridines reacted smoothly under suitably combined Lewis acid/Brønsted base catalysis.
双核席夫碱催化下马来酸盐对氮丙啶的区域发散平行动力学拆分。区域发散反应在催化剂控制下进行，与氮丙啶上的取代基无关，使用 Y(OTf)3/La(OiPr)3/双核席夫碱=1:1:1 的混合物，用量为 2.5-10 mol%，可得到 96→>99.5%ee 的各种γ-氨基酸衍生物。不仅末端氮丙啶，而且内消旋氮丙啶在合适的路易斯酸/布朗斯台德碱催化下也能顺利反应。
