The Versatile and Strategic O‑Carbamate Directed Metalation Group in the Synthesis of Aromatic Molecules: An Update

The aryl O-carbamate (ArOAm) group is among the strongest of the directed metalation groups (DMGs) in directed ortho metalation (DoM) chemistry, especially in the form Ar-OCONEt2. Since the last comprehensive review of metalation chemistry involving ArOAms (published more than 30 years ago), the fie...

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Bibliographic Details
Published in:Chemical reviews 2024-06, Vol.124 (12), p.7731-7828
Main Authors: Jansen-van Vuuren, Ross D., Liu, Susana, Miah, M. A. Jalil, Cerkovnik, Janez, Košmrlj, Janez, Snieckus, Victor
Format: Article
Language:English
Subjects:
Aromatic compounds
Chemical synthesis
Cross coupling
Substrates
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Summary:The aryl O-carbamate (ArOAm) group is among the strongest of the directed metalation groups (DMGs) in directed ortho metalation (DoM) chemistry, especially in the form Ar-OCONEt2. Since the last comprehensive review of metalation chemistry involving ArOAms (published more than 30 years ago), the field has expanded significantly. For example, it now encompasses new substrates, solvent systems, and metalating agents, while conditions have been developed enabling metalation of ArOAm to be conducted in a green and sustainable manner. The ArOAm group has also proven to be effective in the anionic ortho-Fries (AoF) rearrangement, Directed remote metalation (DreM), iterative DoM sequences, and DoM-halogen dance (HalD) synthetic strategies and has been transformed into a diverse range of functionalities and coupled with various groups through a range of cross-coupling (CC) strategies. Of ultimate value, the ArOAm group has demonstrated utility in the synthesis of a diverse range of bioactive and polycyclic aromatic compounds for various applications.
ISSN:0009-2665
1520-6890
1520-6890
DOI:10.1021/acs.chemrev.3c00923