Phenylboronic acid esters of the common 2-deoxy-aldoses

Phenylboronic acid esters are formed by the three common 2-deoxy aldoses: 2-deoxy-D-erythro-pentose ('2-deoxy-D-ribose'), 2-deoxy-D-lyxo-hexose ('2-deoxy-D-galactose'), and 2-deoxy-D-arabino-hexose ('2deoxy-D-glucose'). The major species that was formed from equimolar quantities of boronic acid and the aldose, was the 3,4-monoester of the pentopyranose in a skew-boat conformation, and the 4,6-monoester in the case of the two hexopyranoses. A double molar quantity of boronic acid led, for both 2-deoxyhexoses, to the diester of the open-chain aldehydo isomer as the major product: the 3,5: 4,6-diester for the lyxo-configured deoxy-hexose, and the 3,4:5,6-diester of the arabino-configured isomer. Minor products of all reactions were identified by a combined NMR/DFT methodology. (C) 2011 Elsevier Ltd. All rights reserved.