Chéry Florence, Cabianca Elena, Tatibouët Arnaud, De Lucchi Ottorino, Lindhorst Thisbe K, Rollin Patrick
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.
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。
