A convenient protocol has been developed for the synthesis of Baylis–Hillman adducts in the presence of a base and an organocatalyst. We have designed and synthesized organocatalysts based on hydrogen bonding using a pyrrolidine ring as the backbone and applied them to Baylis–Hillman transformations. This method provides products in good to high yields (73–90%) and with excellent enantiomeric excesses (up to 96%) and ...