Directed Remote Lateral Metalation: Highly Substituted 2-Naphthols and BINOLs by in situ Directing Group Generation

Snieckus, Victor; Kitching, Matthew; Laars, Marju; Board, Johnathan; Patel, Jignesh; Gan, Wei

Abstract

A general synthesis of highly substituted 2‐naphthols based on a new carbanionic reaction sequence is demonstrated. The reaction exploits the dual nature of lithium bases consisting of consecutive ring opening of readily available coumarins with LiNEt2 or LDA to Z‐cinnamamides generating a directing group in situ and allowing, by conformational freedom, a lateral directed remote metalation ‐ ring closure reaction to give the aryl 2‐naphthols in good to excellent yields. These transformations can be combined to provide a more efficient one pot process. Mechanistic insight into the remote lateral metalation step demonstrating the requirement of Z‐cinnamamide is described. Application of this methodology to the synthesis of highly substituted 3,3'‐diaryl BINOL ligands is also reported.

Citation

Snieckus, V., Kitching, M., Laars, M., Board, J., Patel, J., & Gan, W. (2018). Directed Remote Lateral Metalation: Highly Substituted 2-Naphthols and BINOLs by in situ Directing Group Generation. Angewandte Chemie, 130(30), 9569-9573. https://doi.org/10.1002/ange.201805203

• Journal Article Type: Article
• Acceptance Date: May 30, 2018
• Online Publication Date: Jun 21, 2018
• Publication Date: Jul 20, 2018
• Deposit Date: Jun 4, 2018
• Publicly Available Date: Jun 4, 2018
• Journal: Angewandte Chemie
• Print ISSN: 0044-8249
• Electronic ISSN: 1521-3757
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 130
• Issue: 30
• Pages: 9569-9573
• DOI: https://doi.org/10.1002/ange.201805203
• Public URL: https://durham-repository.worktribe.com/output/1329610