Modular bismacycles for the selective C–H arylation of phenols and naphthols

Jurrat, Mark; Maggi, Lorenzo; Lewis, William; Ball, Liam T.

Abstract

Given the important role played by 2-hydroxybiaryls in organic, medicinal and materials chemistry, concise methods for the synthesis of this common motif are extremely valuable. In seeking to extend
the synthetic chemists’ lexicon in this regard, we have developed an expedient and general strategy for the ortho-arylation of phenols and naphthols using readily-available boronic acids. Our methodology relies on in situ generation of a uniquely reactive Bi(V) arylating agent from a bench stable Bi(III) precursor via telescoped B-to-Bi transmetallation and oxidation. By exploiting reactivity 2
that is orthogonal to conventional metal-catalyzed manifolds, diverse aryl and heteroaryl partners can be rapidly coupled to phenols and naphthols under mild conditions. Following arylation, high
yielding recovery of the Bi(III) precursor allows for its efficient re-use in subsequent reactions. Mechanistic interrogation of each key step of the methodology informs its practical application and
provides fundamental insight into the under-exploited reactivity of organobismuth compounds.

Citation

Jurrat, M., Maggi, L., Lewis, W., & Ball, L. T. (2020). Modular bismacycles for the selective C–H arylation of phenols and naphthols. Nature Chemistry, 12(3), 260-269. https://doi.org/10.1038/s41557-020-0425-4

• Journal Article Type: Article
• Acceptance Date: Jan 21, 2020
• Online Publication Date: Feb 27, 2020
• Publication Date: 2020-03
• Deposit Date: Feb 28, 2020
• Publicly Available Date: Aug 28, 2020
• Journal: Nature Chemistry
• Print ISSN: 1755-4330
• Electronic ISSN: 1755-4349
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Issue: 3
• Pages: 260-269
• DOI: https://doi.org/10.1038/s41557-020-0425-4
• Keywords: General Chemistry; General Chemical Engineering
• Public URL: https://nottingham-repository.worktribe.com/output/4050294
• Publisher URL: https://www.nature.com/articles/s41557-020-0425-4
• Additional Information: Received: 20 March 2019; Accepted: 21 January 2020; First Online: 27 February 2020; : Bismacycle InternalRef removed has been made commercially available via Key Organics. The sales revenue that is returned to the University of Nottingham covers the costs of commercialization; the authors do not receive profit from any of the sales that are made.