A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilova St. 28, Moscow 119991, Russian Federation.
National Research University Higher School of Economics, Miasnitskaya Str. 20, Moscow 101000, Russian Federation.
J Org Chem. 2022 Sep 16;87(18):12182-12195. doi: 10.1021/acs.joc.2c01339. Epub 2022 Sep 7.
Nowadays, design of the new chiral ligands for organometallic catalysts is often based on the step-by-step increase in their complexity to improve efficiency. Herein we describe that simple in situ addition of the fluoride source to the asymmetric organometallic catalyst can improve not only activity but also enantioselectivity. Bromide-nickel diimine complexes were found to catalyze asymmetric Michael addition in low yields and ee, but activation with fluoride leads to a significant improvement in catalyst performance. The developed approach was applied to prepare several enantioenriched GABA analogues.
如今，新型手性配体的设计通常基于逐步增加其复杂性以提高效率。在此，我们描述了向不对称金属有机催化剂中简单地原位添加氟源不仅可以提高活性，而且可以提高对映选择性。溴化镍二亚胺配合物被发现以低产率和 ee 催化不对称迈克尔加成，但用氟化物激活会显著改善催化剂性能。所开发的方法被用于制备几种手性富集的 GABA 类似物。
