[摘要]:A secondary amine-amide organocatalyst (e.g., L-pipecolic acid deriv. with (R,R)-1,2-diphenylethylenediamine backbone) has been applied in the asym. Henry reaction of a-ketophosphonates. A series of arom., heteroarom., and aliph. a-ketophosphonates can be converted into the desired a-hydroxy-b-nitrophosphonates in moderate to high yields with excellent enantioselectivities (up to 99% ee) under mild conditions. The mechanism of reaction was investigated by theor. calcns.