Chiral, non-racemic hexahydro-oxazolo[3,2-a]pyridin-5-ones are strategic starting materials for the asymmetric synthesis of alkaloids, via the stereoselective C-C bond formation at the position a to the nitrogen atom. The stereoselectivity of this key step is mainly driven by the geometry of the fused rings of the oxazolopyridine moiety. In this work, the synthesis and X-ray structure of trans(3R,2aS)-(-)-3-phenyl-hexahydro-oxazolo[3,2-a]pyridin-5-one is reported.