Chiral Imines on the Wave: Reactivity of tert-Butyl Acrylate and Stereoselectivity Determination Using NMR in Liquid Crystals

In connection with synthetic applications, we have foreseen to study the reactivity of the poorly reactive tert-butyl acrylate electrophile with chiral imines of unsymmetrical ketones, using conventional or microwave flash heating under carefully controlled reaction conditions in order to develop a very quick and efficient access to the corresponding Michael adducts in which a created stereogenic quaternary carbon center was fully stereocontrolled. Depending on the conditions, either a keto ester or a lactam were obtained. A good correlation was obtained between experiment and theoretical calculations. . The stereoselectivity of the process (e>95%)  was determined using natural abundance ¹³C-{¹H} NMR in a chiral polypeptide liquid crystal.