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Synthesis of Multifunctional Aryl(trifloxyalkenyl)iodonium Triflate Salts.

ABSTRACT: A convenient procedure for the synthesis of aryl(trifloxyalkenyl)iodonium triflate salts from commercially available (diacetoxyiodo)benzene, trimethylsilyl trifluoromethanesulfonate, and acetylenes under mild conditions was developed. The obtained multifunctional hypervalent vinyliodonium salts equipped with electrophilic and nucleophilic functions could serve as novel C2 synthons for organic transformations. The structure of the iodonium salts was identified by multidimensional NMR spectroscopy and X-ray crystallography.

SUBMITTER: Toth BL

PROVIDER: S-EPMC6648789 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Copper-catalyzed [18F]fluorination of (mesityl)(aryl)iodonium salts.

Project description:A practical, rapid, and highly regioselective Cu-catalyzed radiofluorination of (mesityl)(aryl)iodonium salts is described. This protocol utilizes [(18)F]KF to access (18)F-labeled electron-rich, -neutral, and -deficient aryl fluorides under a single set of mild conditions. This methodology is applied to the synthesis of protected versions of two important radiotracers: 4-[(18)F]fluorophenylalanine and 6-[(18)F]fluoroDOPA.

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Efficient Pathway for the Preparation of Aryl(isoquinoline)iodonium(III) Salts and Synthesis of Radiofluorinated Isoquinolines.

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| S-EPMC5175407 | biostudies-literature

One-pot synthesis and applications of N-heteroaryl iodonium salts.

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Project description:The strategic incorporation of the trifluoromethyl (CF3) functionality within therapeutic or agrochemical agents is a proven strategy for altering their associated physicochemical properties (e.g., metabolic stability, lipophilicity, and bioavailability). Electrophilic trifluoromethylation has emerged as an important methodology for installing the CF3 moiety onto an array of molecular architectures, and, in particular, CF3 ?(3)-iodanes have garnered significant interest because of their unique reactivity and ease of handling. Trifluoromethylations mediated by these hypervalent iodine reagents often require activation through an exogenous Lewis or Brønsted acid; thus, putative intermediates invoked in these transformations are cationic CF3 iodoniums. These iodoniums have, thus far, eluded isolation and investigation of their innate reactivity (which has encouraged speculation that such species cannot be accessed). A more complete understanding of the mechanistic relevance of CF3 iodoniums is paramount for the development of new trifluoromethylative strategies involving ?(3)-iodanes. Here, we demonstrate that CF3 iodonium salts are readily prepared from common ?(3)-iodane precursors and exhibit remarkable persistence under ambient conditions. These reagents are competent electrophiles for a variety of trifluoromethylation reactions, and their reactivity is reminiscent of that observed when CF3 iodanes are activated using Lewis acids. As such, our results suggest the mechanistic relevance of CF3 iodonium intermediates in trifluoromethylative processes mediated by ?(3)-iodanes. The isolation of CF3 iodonium salts also presents the unique opportunity to employ them more generally as mechanistic probes.

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Automated synthesis of 18F radiolabelled indole containing Oncrasin-like molecules; a comparison of iodonium salts and boronic ester chemistry.

Project description:BACKGROUND:Oncrasin-1 is a small molecule which was identified from a screen of KRAS mutant cancer cells and has shown specificity for KRAS mutant cell killing. We aimed to develop a radiolabelled form of Oncrasin-1 to enable in-vivo imaging of mutant KRAS expression in malignant tumours. This work outlines the synthesis of 3 fluorinated derivatives and development of iodonium salt and boronic ester precursors for radiolabelling with the 18F isotope. RESULTS:In our hands, synthesis of iodonium salts were not easily accessible due to the 3-carbaldehyde indole structure being preferentially oxidized by conditions required for iodonium salt formation, rather than benzyl iodide. Synthesis and radiolabelling of boronic acid pinacol ester precursors were successful, with the products being obtained in yields of 10.76%?±?0.96% (n?=?5), 14.7% ±8.58% (n?=?3) and 14.92% ±3.9% (n?=?3) for 18F KAM001, 18F KAM002 and 18F KAM003 respectively, with radiochemical purity of greater than 99%. CONCLUSIONS:The successful synthesis of these tracers has been undertaken utilizing boronic ester radio-fluorination methods and will allow for investigation of Oncrasin based molecules as potential diagnostics for cancers expressing mutant KRAS protein.

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