Tietze L F, Seele R, Leiting B, Krach T
Institut für Organische Chemie der Georg-August-Universität, Göttingen, F.R.G.
Carbohydr Res. 1988 Sep 15;180(2):253-62. doi: 10.1016/0008-6215(88)80082-x.
The reaction of methyl 2,3,4,6-tetra-O-acetyl-1-O-trimethylsilyl-beta- and -alpha-D-glucopyranuronate severally with the dimethyl or diethyl acetals of formaldehyde, bromoacetaldehyde, propionaldehyde, 3-benzyloxypropionaldehyde, 5-carboxypentanal, and 2-bromohexanal in the presence of catalytic amounts of trimethylsilyl trifluoromethanesulfonate at -78 degrees gave the corresponding (1-alkoxyalkyl) alpha- and beta-glycosides (acetal-glucopyranosiduronates) with retention of configuration at C-1 in yields of 41-91%. Instead of the dialkyl acetals, the corresponding aldehydes and alkyl trimethylsilyl ether can be used. Deacetylation gave the corresponding methyl (acetal-beta- and -alpha-D-glucopyranosid)uronates in good yield. De-esterification of methyl [(1R)-1-methoxybutyl beta-D-glucopyranosid]uronate with esterase gave the acetal-beta-D-glucopyranosiduronic acid which was an excellent substrate for beta-D-glucuronidase.
2,3,4,6-四-O-乙酰基-1-O-三甲基甲硅烷基-β-D-吡喃葡萄糖醛酸甲酯和α-D-吡喃葡萄糖醛酸甲酯分别与甲醛、溴乙醛、丙醛、3-苄氧基丙醛、5-羧基戊醛和2-溴己醛的二甲基或二乙基缩醛，在催化量的三甲基甲硅烷基三氟甲磺酸酯存在下，于-78℃反应，得到相应的(1-烷氧基烷基)α-和β-糖苷(缩醛-吡喃葡萄糖醛酸酯)，C-1位构型保持不变，产率为41-91%。除了二烷基缩醛外，也可以使用相应的醛和烷基三甲基甲硅烷基醚。脱乙酰化以良好的产率得到相应的甲基(缩醛-β-和-α-D-吡喃葡萄糖苷)醛酸酯。[(1R)-1-甲氧基丁基-β-D-吡喃葡萄糖苷]醛酸甲酯用酯酶进行脱酯化反应，得到缩醛-β-D-吡喃葡萄糖醛酸，它是β-D-葡萄糖醛酸酶的优良底物。
