A new synthetic route for axially chiral secondary amines with binaphthyl backbone and their applications in asymmetric Michael reaction of aldehydes to nitroalkenes.

A new synthetic route for binaphthyl-based secondary amines has been developed. The key features of this route include the selective direct esterification of the binaphthyl structure at the 3- or 3,3'-position and the methylation by a Negishi cross-coupling reaction. Based on the new approach, a series of 3-monosubstituted and 3,3'-disubstituted chiral secondary amines with a binaphthyl backbone were synthesized and screened in the Michael reaction of aldehydes to various nitroalkenes. 3-Monosubstituted secondary amine 7c was proved to be the best catalyst, affording high yields (up to 95%), good to excellent enantioselectivities (up to 99%) and diastereoselectivities (syn/anti up to 99:1) under the optimized conditions. This journal is © The Royal Society of Chemistry 2012