Selective demethylation of O -aryl glycosides by iridium-catalyzed hydrosilylation
Selective demethylation of O -aryl glycosides by iridium-catalyzed hydrosilylation
复制标题
铱催化硅氢加成选择性去甲基化 O-芳基糖苷
DOI：
10.1039/d1cc00496d
复制
发表时间：
2021
影响因子：
4.9
通讯作者：
Schley, Nathan D.
中科院分区：
文献类型：
--
作者：
Jones, Caleb A.;Schley, Nathan D.
通过氢化硅烷化裂解烷基醚是用于产生甲硅烷基醚的强有力的合成工具。以前尝试将这种转化应用于碳水化合物衍生物受到选择性差和异头位置优先还原的限制。发现O-芳基糖苷在铱和硼烷催化的氢化硅烷化条件下是稳定的，允许烷基醚裂解而不损失端基官能度。一种阳离子双（膦）铱配合物催化多种2，3，4-三-O-甲基吡喃糖的选择性3-脱甲基反应，提供了一种制备3-羟基或3-乙酰基2，4-二-O-甲基吡喃糖的独特方法。
The cleavage of alkyl ethers by hydrosilylation is a powerful synthetic tool for the generation of silyl ethers. Previous attempts to apply this transformation to carbohydrate derivatives have been constrained by poor selectivity and preferential reduction of the anomeric position. O-Aryl glycosides are found to be stable under iridium- and borane-catalyzed hydrosilylation conditions, allowing for alkyl ether cleavage without loss of anomeric functionality. A cationic bis(phosphine)iridium complex catalyzes the selective 3-demethylation of a variety of 2,3,4-tri-O-methyl pyranoses, offering a unique approach to 3-hydroxy or 3-acetyl 2,4-di-O-methylpyranoses.