6533b7d8fe1ef96bd126a499

RESEARCH PRODUCT

Ortho -Functionalized Aryltetrazines by Direct Palladium-Catalyzed C−H Halogenation: Application to Fast Electrophilic Fluorination Reactions

Julien RogerJean-cyrille HiersoJean-cyrille HiersoRichard A. DecréauChristelle TestaElodie GigotSemra Genc

subject

weak-coordinationbond fluorination412chemistry.chemical_elements-tetrazines010402 general chemistrychemistry01 natural sciences5-tetrazines[ CHIM ] Chemical SciencesCatalysisCatalysiscycloadditionsTetrazinechemistry.chemical_compoundhalogenationfluorineOrganic chemistryMolecule[CHIM]Chemical SciencesmoleculesC-H activationheterocycles010405 organic chemistryElectrophilic fluorinationHalogenationGeneral ChemistrypalladiumCombinatorial chemistry0104 chemical scienceschemistryimaging probesElectrophilecellsfluorescenceSelectivityPalladium

description

International audience; A general catalyzed direct C-H functionalization of s-tetrazines is reported. Under mild reaction conditions, N-directed ortho-C-H activation of tetrazines allows the introduction of various functional groups, thus forming carbon-heteroatom bonds: C-X (X=I, Br, Cl) and C-O. Based on this methodology, we developed electrophilic mono- and poly-ortho-fluorination of tetrazines. Microwave irradiation was optimized to afford fluorinated s-aryltetrazines, with satisfactory selectivity, within only ten minutes. This work provides an efficient and practical entry for further accessing highly substituted tetrazine derivatives (iodo, bromo, chloro, fluoro, and acetate precursors). It gives access to ortho-functionalized aryltetrazines which are difficult to obtain by classical Pinner-like syntheses.

https://hal-univ-bourgogne.archives-ouvertes.fr/hal-01399085