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Isolable fluorinated triphenylmethyl cation salts of [HCB₁₁Cl₁₁]^-: demonstration of remarkable hydride affinity.

ABSTRACT: Significantly fluorinated triarylmethyl cations have long attracted attention as potentially accessible highly reactive carbocations, but their isolation in a convenient form has proved elusive. We show that abstraction of chloride with a cationic silylium reagent leads to the facile formation of di-, tetra-, and hexafluorinated trityl cations, which could be isolated as analytically pure salts with the [HCB₁₁Cl₁₁]^- counterion and are compatible with (halo)arene solvents. The F₆Tr⁺ cation carrying six meta-F substituents was computationally predicted to possess up to 20% higher hydride affinity than the parent triphenylmethyl cation Tr⁺. We report that indeed F₆Tr⁺ displays reactivity unmatched by Tr⁺. F₆Tr⁺ at ambient temperature abstracts hydrides from the C-H bonds in tetraethylsilane, mesitylene, methylcyclohexane, and catalyzes Friedel-Crafts alkylation of arenes with ethylene, while Tr⁺ does none of these.

SUBMITTER: Gunther SO

PROVIDER: S-EPMC9067617 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Isolable fluorinated triphenylmethyl cation salts of [HCB11Cl11]-: demonstration of remarkable hydride affinity.

Gunther S Olivia SO Lee Chun-I CI Song Ellen E Bhuvanesh Nattamai N Ozerov Oleg V OV

Chemical science 20220404 17

Significantly fluorinated triarylmethyl cations have long attracted attention as potentially accessible highly reactive carbocations, but their isolation in a convenient form has proved elusive. We show that abstraction of chloride with a cationic silylium reagent leads to the facile formation of di-, tetra-, and hexafluorinated trityl cations, which could be isolated as analytically pure salts with the [HCB11Cl11]- counterion and are compatible with (halo)arene ...[more]

PMID: 35655874

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Project description:BackgroundThe β-amyloid radiotracer [11C] PiB is extensively used for the Positron Emission Tomography (PET) diagnosis of Alzheimer's Disease and related dementias. For clinical use, [11C] PiB is produced using the 11C-methylation method ([11C] Methyl iodide or [11C] methyl triflate as 11C-methylation agents), which represents the most employed 11C-labelling strategy for the synthesis of 11C-radiopharmaceuticals. Recently, the use of direct [11C]CO2 fixation for the syntheses of 11C-tracers has gained interest in the radiochemical community due to its importance in terms of radiochemical versatility and for permitting the direct employment of the cyclotron-produced precursor [11C]CO2. This paper presents an optimised alternative one-pot methodology of [11C]CO2 fixation-reduction for the rapid synthesis of [11C] PiB using an automated commercial platform and its quality control.Results[11C] PiB was obtained from a (25.9 ± 13.2)% (Average ± Variation Coefficient, n = 3) (end of synthesis, decay corrected) radiochemical yield from trapped [11C]CO2 after 1 min of labelling time using PhSiH3 / TBAF as the fixation-reduction system in Diglyme at 150 °C. The radiochemical purity was higher than 95% in all cases, and the molar activity was (61.4 ± 1.6) GBq/μmol. The radiochemical yield and activity (EOS) of formulated [11C] PiB from cyclotron-produced [11C]CO2 was (14.8 ± 12.1)%, decay corrected) and 9.88 GBq (± 6.0%), respectively. These are higher values compared to that of the 11C-methylation method with [11C]CH3OTf (~ 8.3%).ConclusionsThe viability of the system PhSiH3 / TBAF to efficiently promote the radiosynthesis of [11C] PiB via direct [11C]CO2 fixation-reduction has been demonstrated. [11C] PiB was obtained through a fully automated radiosynthesis with a satisfactory yield, purity and molar activity. According to the results, the one-pot methodology employed could reliably yield sufficiently high tracer amounts for preclinical and clinical use.

Dataset Information

Isolable fluorinated triphenylmethyl cation salts of [HCB₁₁Cl₁₁]^-: demonstration of remarkable hydride affinity.

Publications

Isolable fluorinated triphenylmethyl cation salts of [HCB<sub>11</sub>Cl<sub>11</sub>]<sup>-</sup>: demonstration of remarkable hydride affinity.

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