Beneficial effect of internal hydrogen bonding interactions on the beta-fragmentation of primary alkoxyl radicals. Two-step conversion of D-xylo- and D-ribofuranoses into L-threose and D-erythrose, respectively |
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Authors: | Hernandez-García Luís Quintero Leticia Sánchez Mario Sartillo-Piscil Fernando |
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Affiliation: | Centro de Investigación de la Facultad de Ciencias Químicas, BUAP, 14 Sur Esq. San Claudio, Col. San Manuel, 72570, Puebla, México. |
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Abstract: | Primary alkoxyl free radicals were generated from their readily synthesized N-phthalimido derivatives under reductive conditions. Primary alkoxyl radicals derived from their corresponding xylo- and ribofuranose derivatives underwent, exclusively, an unusual beta-fragmentation affording L-threose and D-erythrose derivatives, respectively. This occurs because the alkoxyl radical is capable of achieving an internal hydrogen-bonding interaction leading to a stable six-membered ring intramolecular hydrogen-bonded structure. When the hydroxyl group is protected, the beta-fragmentation pathway is prevented and the hydrogen atom transfer (HAT) pathway occurs. Computational studies provided strong support for the experimental observations. |
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