Institut für Pharmazeutische Wissenschaften, Wolfgang-Pauli-Str. 10, ETH-Hönggerberg HCI, CH-8093, Zürich, Switzerland.
Org Biomol Chem. 2011 Aug 7;9(15):5541-6. doi: 10.1039/c1ob05373f. Epub 2011 Jun 22.
Selectively 6-fluorinated analogs of the tumor-associated T(N) antigen Fmoc-Thr(α-O-GalNAc)-OtBu can be efficiently prepared using DAST-mediated de(hydr)oxyfluorination reactions of preformed and orthogonally protected glycosyl amino esters without affecting the labile protecting groups and O-glycosidic linkages. The resulting mono- and difluorinated T(N) analogs are interesting building blocks for non-hydrolyzable mucin-type antigen mimetics, as illustrated by the unprecedented synthesis of two different multiply fluorinated Thomsen-Friedenreich derivatives. The reported deoxyfluoro antigen analogs represent important functional probes for carbohydrate-binding proteins and glycosyl-processing enzymes.
使用 DAST 介导的预形成和正交保护的糖基氨基酯的去（水）氟氯化反应，可以有效地制备肿瘤相关 T（N）抗原 Fmoc-Thr（α-O-GalNAc）-OtBu 的选择性 6-氟代类似物，而不会影响不稳定的保护基团和 O-糖苷键。所得的单氟和二氟代 T（N）类似物是不可水解粘蛋白型抗原类似物的有趣构建块，如前所未有的两种不同的多氟代 Thomsen-Friedenreich 衍生物的合成所示。报道的脱氧氟代抗原类似物是糖结合蛋白和糖基化酶的重要功能探针。
