Peczuh Mark W, Snyder Nicole L, Sean Fyvie W
Department of Chemistry, The University of Connecticut, 55 North Eagleville Road, Storrs, CT 06269, USA.
Carbohydr Res. 2004 Apr 28;339(6):1163-71. doi: 10.1016/j.carres.2004.01.022.
The synthesis and X-ray crystal structure of a D-xylose-based oxepine are reported. The oxepine was prepared from 2,3,4-tri-O-benzyl-D-xylose by the three-step sequence (Wittig olefination, vinyl ether formation, and ring closing metathesis) we recently reported. Epoxidation of this cyclic enol ether using dimethyldioxirane (DMDO) gave 1,2-anhydro-beta-D-idoseptanose, which was trapped by a number of nucleophiles to give alpha-idoseptanosides. The stereochemistry of epoxidation was assigned based on product analysis. Spectroscopic data of methyl 2,3,4,5-tetra-O-acetyl-alpha-D-idoseptanoside, derived from the methanolysis product 11, was compared to data of its enantiomer, the known methyl 2,3,4,5-tetra-O-acetyl-alpha-L-idoseptanoside.
报道了一种基于D-木糖的氧杂环庚三烯的合成及其X射线晶体结构。该氧杂环庚三烯是由2,3,4-三-O-苄基-D-木糖通过我们最近报道的三步序列（维蒂希烯烃化、乙烯基醚形成和闭环复分解）制备的。使用二甲基二氧杂环丙烷（DMDO）对该环状烯醇醚进行环氧化反应得到1,2-脱水-β-D-艾杜庚糖，它被多种亲核试剂捕获得到α-艾杜庚糖苷。基于产物分析确定了环氧化反应的立体化学。将源自甲醇解产物11的2,3,4,5-四-O-乙酰基-α-D-艾杜庚糖苷甲酯的光谱数据与其对映体、已知的2,3,4,5-四-O-乙酰基-α-L-艾杜庚糖苷甲酯的数据进行了比较。
