title: Synthesis of fluorinated Thomsen-Friedenreich antigens: direct deoxyfluorination of αGalNAc-threonine tert-butyl esters.
abstract: 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.
authors.affiliation: Institut für Pharmazeutische Wissenschaften, Wolfgang-Pauli-Str. 10, ETH-Hönggerberg HCI, CH-8093, Zürich, Switzerland.
authors.forename: Manuel
authors.initials: M
authors.lastname: Johannes
authors.forename: Thomas
authors.initials: T
authors.lastname: Oberbillig
authors.forename: Anja
authors.initials: A
authors.lastname: Hoffmann-Röder
mesh_terms: D000116:Acetylgalactosamine / Q000737:chemistry*; D015295:Antigens, Tumor-Associated, Carbohydrate / Q000737:chemistry*; D005456:Fluorescent Dyes / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D013912:Threonine / Q000737:chemistry*
chemical_list: D015295:Antigens, Tumor-Associated, Carbohydrate; D005456:Fluorescent Dyes; D005461:Fluorine; D013912:Threonine; C016467:Thomsen-Friedenreich antigen; D000116:Acetylgalactosamine