2,3-O-亚苄基-6-脱氧-α-L-甘露吡喃糖苷衍生物与丁基锂的反应：2,6-二脱氧-4-O-甲基-α-L-赤藓糖己吡喃糖苷-3-酮的合成

Reaction of derivatives of methyl 2,3-O-benzylidene-6-deoxy-alpha-L-mannopyranoside with butyllithium: synthesis of methyl 2,6-dideoxy-4-O-methyl-alpha-L-erythro-hexopyranosid-3-ulose.

作者信息

Clode D M, Horton D, Weckerle W

出版信息

Carbohydr Res. 1976 Jul;49:305-14. doi: 10.1016/s0008-6215(00)83147-x.

Abstract

Methyl 2,3-O-benzylidene-6-deoxy-alpha-L-mannopyranoside (2) reacted with butyllithium to give a mixture of 1,5-anhydro-3-C-butyl-1,2,6-trideoxy-L-ribo-hex-1-enitol (3) and its L-arabino analogue (4), together with methyl 2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside (5). In contrast, the 4-O-methyl-analogue (8) of 2 was converted by butyllithium into methyl 2,6-dideoxy-4-O-methyl-alpha-L-erythro-hexo-pyranosid-3-ulose (9), which was further characterized as its oxime 10. The 4-O-benzyl analogue of 8, obtained as two separate diastereoisomers (6 and 7) differing in configuration at C-2 of the dioxolane ring gave a complex misture of products on treatment with butyllithium.

摘要

2,3 - O - 亚苄基 - 6 - 脱氧 - α - L - 甘露吡喃糖苷（2）与丁基锂反应，生成1,5 - 脱水 - 3 - C - 丁基 - 1,2,6 - 三脱氧 - L - 核糖 - 己 - 1 - 烯醇（3）及其L - 阿拉伯糖类似物（4）的混合物，以及2,3,6 - 三脱氧 - α - L - 赤藓糖 - 己 - 2 - 烯吡喃糖苷（5）。相比之下，2的4 - O - 甲基类似物（8）被丁基锂转化为2,6 - 二脱氧 - 4 - O - 甲基 - α - L - 赤藓糖 - 己 - 吡喃糖苷 - 3 - 酮（9），其进一步被表征为其肟10。8的4 - O - 苄基类似物以两种在二氧戊环环C - 2构型不同的单独非对映异构体（6和7）形式获得，在用丁基锂处理时得到复杂的产物混合物。