On the Thermodynamically Controlled Epimerization of Deoxynitroinositol Monomethyl Ethers

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Abstract
1-Deoxy-4-O-methyl-1-nitro-scyllo-inositol (1), its myo-1 epimer (2), 3-deoxy-6-O-methyl-3-nitro-epi-inositol (3), and its muco-3 epimer (4) in the presence of excess base give nitronates (1′ from 1, 2′ from 2, and 3′ from 3 and 4) which are mutually interconverted by epimerization. The equilibrium constants were determined, revealing the order of thermodynamic stabilities of the nitronates to be 3′ > 2′ > 1′. In the presence of a catalytic amount of base, the nitro inositols epimerize also, and the order of stability of the free nitro compounds is [Formula: see text]. The connection between these epimerizssation equilibria and the pKa values of the compounds is discussed. The results are explained in terms of conformational analysis, whereby the importance of the A(1,3) strain is reasserted and good agreement with calculated conformational energy data is obtained.

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