Ferroceneboronic Acid and Derivatives Synthesis, Structure, Electronic Properties, and Reactivity in Directed C-H Bond Activation

Abstract : Known since 1959, ferroceneboronic acid (1) and its derivatives have been mainly used as polyol sensors and in cross-coupling reactions. However, a literature survey revealed that there is not a paper describing the full characterization of ferroceneboronic acid derivatives and that useful boron protecting groups have not been studied in the ferrocene series. Here, we present an optimized multigram-scale synthesis of the known ferroceneboronic acid (1) using a phase-switch purification process. It was furthermore functionalized to reach the diaminonaphthalene (FcB(dan), 15), anthranilamides (FcB(aam), 16; FcB(Me-aam), 17 and 18), potassium trifluoroborate (FcBF3K, 19), triolborate (FcB(triolborate), 20) and N-methyliminodiacetic acid (FcB(MIDA), 21) derivatives. Their structures were unambiguously assigned by NMR and X-ray analysis, and the data collected provided a general overview of the electronic and structural features of these compounds. From the data obtained, B(dan) and B(amm) were classified as electron-withdrawing groups, whereas trifluoroborate and triolborate behave as electron-donating groups. We report the first catalytic silylation of ferrocene C-H bonds to access di- and trisubstituted derivatives. Catalytic borylation was also attempted, highlighting a switch in regioselectivity that was unambiguously assigned by X-ray analysis.
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Organometallics, 2018, 37 (21), pp.3780-3790. 〈10.1021/acs.organomet.8b00501〉
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Contributeur : Laurent Jonchère <>
Soumis le : vendredi 14 décembre 2018 - 15:48:48
Dernière modification le : jeudi 17 janvier 2019 - 01:18:05

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W. Erb, J.-P. Hurvois, T. Roisnel, V. Dorcet. Ferroceneboronic Acid and Derivatives Synthesis, Structure, Electronic Properties, and Reactivity in Directed C-H Bond Activation. Organometallics, 2018, 37 (21), pp.3780-3790. 〈10.1021/acs.organomet.8b00501〉. 〈hal-01939028〉

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