Direct Amination via Bifunctional Iridium Amido Complex

Significance

While methods for the enantio­selective direct amination reaction often rely on Lewis acid catalysis and organocatalysis, a limited number of metal-based approaches have been reported. Based on the previous development of a bifunctional ruthenium catalyst for asymmetric Michael reactions (J. Am. Chem. Soc. 2004, 126, 11148), the authors report a bifunctional iridium amido complex for the enantioselective direct amination of α-cyanoacetates using dialkyl diazocarboxylates. A variety of aminated products could be obtained in consistently quantitative yields and excellent enantioselectivities. Interestingly, a related ruthenium complex exhibited low levels of enantioselection.