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The novel chiral spirobipyridopyrans 1 and 2 were synthesized by the acid catalyzed aldol type condensation of 5-deoxypyridoxal with the appropriate ketone and subsequent reaction of the resulting pyrylium salt with base. The indolinospiropyridopyrans 3-5, which contain the modified B(6) unit, were prepared by aldol reaction of 5-deoxypyridoxal with 1,3,3-trimethyl-2-methylenindolines. Analytical separation of enantiomers was accomplished by low-pressure liquid chromatography (LPLC) on triacetylcellulose. The barriers to thermal racemization were determined by on-line measurements of the enriched enantiomers after LPLC. Gibbs energies of activation DeltaG superset, not equals for reversible cleavage of the C(spiro)-O bond in 1, 3, and 4 were in the range 103-108 kJ/mol. The lower limits of the barriers in 2 and 5 were estimated to be greater than 102 and 109 kJ/mol by attempted thermal racemizations. The increase of the barriers from 3 to 4 and 5 was explained by the influence of electron withdrawing groups, which reduce the stability of the ring-opened transition states to C(sp3)-O bond cleavage. Geometrical data from X-ray structure analysis showed that the angle [C3-C2-C3'] around the spiro carbon atom increases with elongation of the chain in the C3-C3' bridge. This angle widening is explained by a ring-strain effect, which is greater in the five-membered ring in the skeleton of 7 than in the six- and seven-membered rings of 1 and 2.