DFT investigations of the isomerization and deprotonation of malononitrile by the amines were performed at the B3LYP/6-31++G** level. Calculations indicate that isomerization of malononitrile is difficult to achieve without promoters because of high energy barriers. Basic N atoms in amines can abstract an H atom from malononitrile. Activation barriers for proton abstraction are highly correlated with the available or estimated pK_a values of protonated amines. The reaction mechanism can be deduced from the slope of the Brönsted plot. This work suggests an efficient catalyst, N-1, based on computational results.