Dardonville Christophe, Gilbert Ian H
Welsh School of Pharmacy, Cardiff University, Redwood Building, King Edward VII Avenue, Cardiff, UK CF10 3XF.
Org Biomol Chem. 2003 Feb 7;1(3):552-9. doi: 10.1039/b210606j.
The synthesis of (2R)-2-methyl-4,5-dideoxy and (2R)-2-methyl-4-deoxy analogues of 6-phosphogluconate is described. The synthetic strategy relies on the Evans aldol reaction for the installation of the chiral centres in the 2- and 3-positions. The selective phosphorylation at the primary alcohol function of (2R,3S)-3,6-dihydroxy-2-methylhexanoic acid benzyl ester (5) and (2R,3S,5S)-3,5,6-trihydroxy-2-methylhexanoic acid benzyl ester (20) was achieved with dibenzyl phosphochloridate and dibenzyl phosphoiodinate respectively, working at low temperature. (2R,3S)-3-Hydroxy-2-methyl-6-phosphonoxyhexanoic acid (9) was obtained in 25% overall yield from 4-benzyloxybutanol and (2R,3S,5S)-3,5-dihydroxy-2-methyl-6-phosphonoxyhexanoic acid (28) in 10% overall yield from L-malic acid.
描述了6-磷酸葡萄糖酸的(2R)-2-甲基-4,5-二脱氧和(2R)-2-甲基-4-脱氧类似物的合成。合成策略依赖于埃文斯醛醇反应来在2-位和3-位引入手性中心。分别使用二苄基磷酰氯和二苄基磷酰碘在低温下实现了(2R,3S)-3,6-二羟基-2-甲基己酸苄酯(5)和(2R,3S,5S)-3,5,6-三羟基-2-甲基己酸苄酯(20)伯醇官能团的选择性磷酸化。(2R,3S)-3-羟基-2-甲基-6-膦酰氧基己酸(9)由4-苄氧基丁醇以25%的总收率得到，(2R,3S,5S)-3,5-二羟基-2-甲基-6-膦酰氧基己酸(28)由L-苹果酸以10%的总收率得到。
