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.
Document type :
Journal articles
Complete list of metadatas

Cited literature [5 references]  Display  Hide  Download

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01939028
Contributor : Laurent Jonchère <>
Submitted on : Friday, December 14, 2018 - 3:48:48 PM
Last modification on : Thursday, February 7, 2019 - 4:55:47 PM
Long-term archiving on : Friday, March 15, 2019 - 12:57:57 PM

Identifiers

Citation

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⟩

Share

Metrics

Record views

30

Files downloads

56