During the synthesis of 3-hydroxy-3-ethinylquinuclidine (I), two additional products were isolated and identified as (E)-3-[2-(3-oxoquinuclidine)]quinuclidylidene (III) and (E)-3-[2-(3-hydroxy-3-ethinylquinuclidine)]quinuclidylidene (V). The base-catalyzed autocondensation of 3-quinuclidinone resulted in the alpha,beta-unsaturated ketone dimer (III) as a single isomer. The geometric configuration was deduced by examination of the NMR spectra of the methyl iodide salt. Compound V was thus the result of attack on the carbonyl carbon of III by the acetylide anion. The isolation and identification of these compounds clarified the reported differences in the physical properties of I and its analogs.