Naturally occurring myo-inositol was developed into a highly rigid diol by converting its 3,4- and 1,6-vicinal diols in trans configuration into the corresponding butane-2,3-diacetals. The resulting diol bearing 6-6-6 fused ring system, in which conformational change is strictly suppressed, was combined with diisocyanates to perform polyadditions. The resulting polyurethanes were analyzed by differential scanning calorimetry, and it was found that their glass transition temperatures were much higher than those of the previously reported myo-inositol-derived polyurethanes, which were synthesized from a myo-inositol-derived diol bearing 5-6-5 fused ring system. (C) 2017 Wiley Periodicals, Inc.