The photolysis of N‐alkylpyridinium halides 9a–e in alkaline H2O gave 6‐azabicyclo[3.1.0]hexenol derivatives 10a–e. N–Substituents bearing ether, acetal, and alcohol functions were found to do not adversely influence the photochemical reaction course. The free OH groups of the N–(3‐hydroxypropyl) derivative 10d were protected by benzoylation. The ensuing dibenzoate 14 underwent stereocontrolled opening of the aziridine ring on reaction with MeSH/BF3 to give a thioether 15. With benzoic acid in CHCI3, 10d gave the 4‐hydroxy‐5‐aminocyclopent‐2‐enyl benzoate 11. The meso‐2‐aminocyclopent‐4‐ene‐1,3‐diol 12 was obtained by hydrolysis of 11. On reaction with Boc2O and NaI, the aziridine ring of 14 was converted to a bicyclic compound 17. Hydrolysis of 17 provided the trans‐1,3‐diol 18, the epimer of 12. Face‐selective dihydroxylation of Boc‐protected 12 gave a meso‐aminocyclopentanetetrol 23 which was characterized upon peracetylation. Dihydroxylation of 15 provided a racemic analogue of epi‐mannostatin A (26).