From L-amino acid, three chiral thiophosphonodiamides were prepared as new hydrogen bond donor organocatalysts. Under the mediation of the catalyst derived from L-valine, a tandem Michael addition/ cyclization reaction between (E)-2-(2-nitrovinyl)phenols and malononitrile proceeds smoothly, giving pharmaceutically valuable 2-amino-4H-chromene-3-carbonitriles in high yields with 66-95% ee within 2 h.