Substituted chiral hydrindanes were synthesized as single isomers in almost enantiopure forms through a one-pot process that proceeds via the diphenylprolinol silyl ether mediated-domino Michael/Michael reaction of alpha,beta-unsaturated aldehydes and 3-hexene-2,5-dione, and a subsequent intramolecular aldol condensation of the generated cyclopentanone intermediate.