Remarkable beta-selectivity in the synthesis of beta-1-C-arylglucosides: stereoselective reduction of acetyl-protected methyl 1-C-arylglucosides without acetoxy-group participation.
Remarkable beta-selectivity in the synthesis of beta-1-C-arylglucosides: stereoselective reduction of acetyl-protected methyl 1-C-arylglucosides without acetoxy-group participation.
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β-1-C-芳基葡糖苷合成中显着的β-选择性：在没有乙酰氧基参与的情况下，乙酰基保护的甲基1-C-芳基葡糖苷的立体选择性还原。
DOI：
10.1021/jo071051i
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发表时间：
2007
期刊：
影响因子：
--
通讯作者：
R. H. Mueller
中科院分区：
文献类型：
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作者：
P. Deshpande;B. Ellsworth;F. Buono;A. Pullockaran;Janak Singh;T. P. Kissick;Mingzhou Huang;Hildegard Lobinger;T. Denzel;R. H. Mueller
得到了一种高效、实用的β-C-芳基葡萄糖苷衍生物的合成方法。所述方法涉及刘易斯酸介导的全乙酰化1-C-芳基甲基葡糖苷的离子还原，所述全乙酰化1-C-芳基甲基葡糖苷衍生自芳基-Li与选择性保护的δ-D-葡内酯的加成。2-乙酰氧基-1-C-氧杂卡宾鎓离子中间体的还原以高度选择性进行，得到没有2-乙酰氧基参与的β-C-芳基葡糖苷。此外，在减少过程中，我们还确定了水的前所未有的关键作用。由于成本和化学相容性问题，通过改变通常的苄基醚保护基，使新方法更加有效和高选择性。
An efficient and practical process to generate beta-C-arylglucoside derivatives was achieved. The process described involves Lewis acid mediated ionic reduction of a peracetylated 1-C-aryl methyl glucoside derived from the addition of an aryl-Li to selectively protected delta-D-gluconolactone. The reduction of the 2-acetoxy-1-C-oxacarbenium ion intermediates proceeds with a high degree of selectivity to give beta-C-arylglucosides without 2-acetoxy group participation. Furthermore, during the reduction process we also identified an unprecedented critical role of water. By changing from the usual benzyl ether protecting groups because of cost and chemical compatibility concerns, the new process is made additionally efficient and highly selective.