1,4-Thiazine, benzo[1,4]thiazine, pyrrolo[1.4]thiazine and their polyhydro derivatives are privileged heterocyclic core present in many bioactive molecules.1-2 Over the past decades, several methods have been developed to construct achiral/racemic pyrrolo[1,4]thiazine derivatives.3 Recently, Feng et al. reported the first synthesis of chiral hydropyrrolo-thiazoles and [1,4]thiazine derivatives using chiral N,N´-dioxide/metal catalysts.4 Herein, we report a proline-derived organocatalytic enantioselective synthesis of pyrrolo[1,2-d][1,4]thiazine-2-carbaldehydes using domino 1,3-dipolar cycloaddition/rearrangement of benzothiazolium salt with α,β-unsaturated aldehyde. This domino process produced fluorescent emissive chiral molecules with three contiguous stereocenters, having one chiral quaternary center in a single step. This strategy was extended to the stereoselective one-pot synthesis of chiral N-phenyl thioether-tethered tetrasubstituted dihydropyrrole-3-carbaldehydes via 1,3- dipolar cycloaddition/rearrangement, followed by ring-opening/C-S bond formation (Scheme 1).