The enantioselective cyclization of the prochiral cyclic substrates1 to7 and26, can be carried out in theneat using S-proline as catalyst. The substrates18 to22 and27 could not be cyclized with S-proline but could be cyclized with a mixture of S-phenylalanine and d-camphorsulphonic acid. The enantioselective cyclization of prochiral acyclic triones45 and47 and also the racemic tricarbonyl compounds54 to57 could also be carried out in theneat using S-proline as catalyst. The optically active enediones obtained in the above cyclizations could also be obtained directly from 1,3-diones or 2-hydroxymethylene cycloalkanones in a one-pot reaction with methyl vinyl ketone (MVK) and S-proline in the absence of solvents.¹³C NMR studies of the one-pot synthesis ofS-11 andS-14 reveal that the annulations involve initial formation of an acid-base complex followed by a Michael reaction and then an enantioselective cyclization. Such enantioselective cyclizations probably occur on the surface of S-proline crystals.