Significance Jørgensen and co-workers demonstrated the potential of unsaturated acyl phosphonates 4 as hydrogen-bond acceptors in enantioselective organocatalysis. By employing chiral thioureas 1 and 2 or squaramide 3 as catalysts, with different carbon-based nucleophiles ( 5 - 7 ), products 8 - 10 were obtained in moderate to good yields and high enantioselectivity.