Fachbereich Chemie, Institut für Pharmazie, Universität Hamburg, Bundesstrasse 45, 20146, Hamburg, Germany.
Angew Chem Int Ed Engl. 2019 Apr 1;58(15):5110-5113. doi: 10.1002/anie.201900995. Epub 2019 Mar 12.
C-Glycosides are carbohydrates that bear a C-C bond to an aglycon at the anomeric center. Due to their high stability towards chemical and enzymatic hydrolysis, these compounds are widely used as carbohydrate mimics in drug development. Herein, we report a general and exclusively β-selective method for the synthesis of a naturally abundant acyl-C-glycosidic structural motif first found in the scleropentaside natural product family. A Corey-Seebach umpolung reaction as the key step in the synthesis of scleropentaside A and analogues enables the β-selective construction of the anomeric C-C bond starting from unprotected carbohydrates in only four steps. The one-pot approach is highly atom-efficient and avoids the use of toxic heavy metals.
C-糖苷是一类在糖苷中心处通过 C-C 键与糖苷配基相连的碳水化合物。由于其对化学和酶水解具有很高的稳定性，这些化合物被广泛用作药物开发中的碳水化合物类似物。在此，我们报告了一种通用且专一地合成天然存在的酰基-C-糖苷结构基序的方法，该基序最初在 scleropentaside 天然产物家族中被发现。Corey-Seebach 反转反应作为合成 scleropentaside A 和类似物的关键步骤，能够从非保护的碳水化合物出发，仅通过四步反应以 β-选择性方式构建糖苷键。该一锅法具有很高的原子经济性，并且避免了使用有毒重金属。
