Diastereoisomers of 4‐hydroxy‐2‐methyl‐3,4‐dihydro‐2H‐pyrano[2,3‐b]quinolines 8 and 9 were synthesized starting from the appropriate 2‐chloroquinoline‐3‐carboxaldehydes 1. The relative configuration of the 1,3‐diol intermediates 4 and 5 was determined on the basis of the 13C‐nmr spectra of their acetonides. The relative stereochemistry of title compounds was confirmed by using homonuclear NOE and selective decoupling experiments, as well as by analysis of the coupling patterns observed in their 1H‐nmr spectra.