A series of 4‐sulfoximinocyclopent‐2‐en‐1‐ones were prepared in 35 to 99% yield through a calcium(II)‐catalyzed aza‐Piancatelli reaction, including in enantioenriched form. Depending on their substitution pattern, diverse diastereoselective chemical transformations can be applied to these scaffolds, allowing access to cyclopentane derivatives. This study opens synthetic routes to cyclopentane‐based scaffolds and also paves the way for the exploration of the associated chemical space in drug discovery.