A set Of C-2-chiral diamines 18-21 based on 1,6-diazacyclodecane have been identified whose conjugate acids are predicted by B3LYP/6-31G(*) calculations to have pK(a) values of similar to 23-6 on the water scale (pKa = 30-33 in MeCN); they are also expected to be kinetically active, but essentially nonnucleophilic. Strain relief on protonation largely determines the basicity of these compounds, and the key to the design of stronger bases is limiting conformational freedom, especially by preventing nitrogen inversion, through the introduction of additional ring fusions. 15,16-Dimethyl-15,16-diazatricyclo[9.3.1.1(4,8)]hexadecane (20) is examined in detail and shown to exist in 10 diastereomeric forms as a result of in-/out-isomerism. The predicted pK(a) values for these diastereomers range over 14 log units.