Tetrafluoroborate (BF 4 À ) has long been used as a spectator counter anion. Herein, we report an unprecedented salt metathesis between a variety of BF 4 À salts and a series of organoboronic acids yielding the corresponding organotrifluoroborates. We identified conditions for fast and efficient fluoridation (< 1 h) with minimal workup. Fundamentally, this work discloses the proclivity of BF 4 À to exchange fluoride atoms with organoboronates, highlighting the lability of BF 4 À .
Organotrifluoroborates have gained acceptance as radioprosthetic groups for radiofluorination. Of these, the zwitterionic prosthetic group “AMBF3” with a quaternary dimethylammonium ion dominates the trifluoroborate space. Herein, we report on imidazolium‐methylene trifluoroborate (ImMBF3) as an alternative radioprosthetic group and report on its properties in the context of a PSMA‐targeting EUK ligand that was previously been conjugated to AMBF3. The ImMBF3 is readily synthesized from imidazole and conjugated via CuAAC “click” chemistry to give a structure similar to PSMA‐617. 18F‐labeling proceeded in one step per our previous reports and imaged in LNCaP‐xenograft bearing mice. The [18F]‐PSMA‐617‐ImMBF3 tracer proved to be less polar (LogP7.4 = −2.95 ± 0.03) while showing a significantly lower solvolytic rate (t1/2 = 8100 min) and slightly higher molar activity (Am) at 174 ± 38 GBq/μmol. Tumor uptake was measured at 13.7 ± 4.8%ID/g and a tumor:muscle ratio of 74.2 ± 35.0, tumor:blood ratio of 21.4 ± 7.0, tumor:kidney ratio of 0.29 ± 0.14, and tumor:bone ratio of 23.5 ± 9.5. In comparison with previously reported PSMA‐targeting EUK‐AMBF3 conjugates, we have altered the LogP7.4 value, tuned the solvolytic half‐life of the prosthetic, and increased radiochemical conversion while achieving similar tumor uptake, contrast ratios, and molar activities compared with AMBF3 bioconjugates.
Salt metathesis ……a nd BFX (boron-fluoride exchange) of BF 4À with boronic acids generates RBF 3 À derivatives,t hus showing the solvolytic lability of BF 4 À that enables its use as a fluorinating agent, even though many highly reactive reagents employ BF 4À as an onreactive counteranion. In their Research Article (e202215371), David M. Perrin and coworkers report the synthesis of RBF 3 À derivatives via asalt metathesis reaction using a series of MBF 4 salts in methanol. This work highlights the proclivity of BF 4 À ,generally considered weakly coordinating and unreactive,torapidly fluorinate boronic acids.
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