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Halogen-directed chemical sialylation: pseudo-stereodivergent access to marine ganglioside epitopes.

ABSTRACT: Sialic acids are conspicuous structural components of the complex gangliosides that regulate cellular processes. Their importance in molecular recognition manifests itself in drug design (e.g. Tamiflu®) and continues to stimulate the development of effective chemical sialylation strategies to complement chemoenzymatic technologies. Stereodivergent approaches that enable the α- or β-anomer to be generated at will are particularly powerful to attenuate hydrogen bond networks and interrogate function. Herein, we demonstrate that site-selective halogenation (F and Br) at C3 of the N-glycolyl units common to marine Neu2,6Glu epitopes enables pseudo-stereodivergent sialylation. α-Selective sialylation results from fluorination, whereas traceless bromine-guided sialylation generates the β-adduct. This concept is validated in the synthesis of HLG-1 and Hp-s1 analogues.

SUBMITTER: Hayashi T

PROVIDER: S-EPMC8152791 | biostudies-literature |

REPOSITORIES: biostudies-literature

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