The first organocatalytic highly enantioselective reactions of substituted <
IMG SRC="/images/gifchars/alpha.gif" BORDER=0>-cyanoacetates and
![](/images/gifchars/beta2.gif)
-dicarbonyl compounds with azodicarboxylates are reported. In the presence of 0.1-5 mol % of a quinidine-derived alkaloid
![](/images/gifchars/beta2.gif)
-ICD, optically active quaternary hydrazine adducts are obtained in very high yields and with enantioselectivities up to >98% ee. A two-step procedure for the cleavage of the hydrazine
N-
N bond using SmI
2 is also demonstrated.