Asymmetric Conjugate Addition of Unmodified Cyclic Ketones to Nitroolefins Using Aminophosphonate as the Organocatalyst

α‐Aminophosphonates are an important class of compounds with diverse and useful biological activities. Despite that their structues are similar to that of proline, however, chiral cyclic α‐aminophosphonates have found little applications in catalytic asymmetric synthesis. In this paper, an enantiopure α‐aminophosphonate has been synthesized and was found to be effective as a chiral organocatalyst for the asymmetric conjugate addition of cycloketones to β‐nitrostyrenes. With a catalyst loading of 20 mol% and in the presence of 10 mol% of CF₃COOH as a cocatalyst, the Michael adducts could be obtained with varying degrees of diastereo‐ and enantioselectivities (up to 97:3 and 90% ee respectively) under solvent‐free conditions.