碳水化合物苯磺酰基亚乙基（PSE）缩醛的还原开环反应。
Reductive opening of carbohydrate phenylsulfonylethylidene (PSE) acetals.
作者信息
Chéry Florence, Cabianca Elena, Tatibouët Arnaud, De Lucchi Ottorino, Lindhorst Thisbe K, Rollin Patrick
机构信息
Université d'Orléans et CNRS, ICOA, UMR 7311, BP 6759, F-45067 Orléans, France.
Université d'Orléans et CNRS, ICOA, UMR 7311, BP 6759, F-45067 Orléans, France; Dipartimento di Chimica, Università Ca'Foscari di Venezia, Dorsoduro 2137, I-30123 Venezia, Italy.
出版信息
Carbohydr Res. 2015 Nov 19;417:117-24. doi: 10.1016/j.carres.2015.09.011. Epub 2015 Sep 26.
The phenylsulfonylethylidene (PSE) acetal is a relatively new protecting group in carbohydrate chemistry. However, carbohydrate-derived phenylsulfonylethylidene (PSE) acetals show a different behavior in reductive desulfonylation than simple symmetrical acetals. Here we have investigated various SET-type reaction conditions in order to open PSE acetals regioselectively and to produce chiral ω-hydroxyethenyl ethers. Whereas sodium amalgam leads to a mixture of regioisomeric vinyl ethers besides the ethylidene acetal, samarium iodide is suited for regioselective ring opening. This is shown with seven different carbohydrate PSE acetals, both of the 1,3-dioxane and the 1,3-dioxolane type.
苯磺酰基亚乙基（PSE）缩醛是碳水化合物化学中一种相对较新的保护基。然而，碳水化合物衍生的苯磺酰基亚乙基（PSE）缩醛在还原脱磺酰化反应中的行为与简单对称缩醛不同。在此，我们研究了各种单电子转移（SET）型反应条件，以便区域选择性地打开PSE缩醛并生成手性ω-羟基乙烯基醚。汞齐钠除了生成亚乙基缩醛外，还会导致区域异构的乙烯基醚混合物，而碘化钐则适用于区域选择性开环。七种不同的1,3-二氧六环型和1,3-二氧戊环型碳水化合物PSE缩醛均证明了这一点。
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