Directed Remote Lateral Metalation: Highly Substituted 2-Naphthols and BINOLs by In Situ Generation of a Directing Group

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

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 either LiNEt2 or LiNiPr2 into Z‐cinnamamides, thus generating a directing group in situ and allowing, by conformational freedom, a lateral directed remote metalation for ring closure 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

Patel, J. J., Laars, M., Gan, W., Board, J., Kitching, M. O., & Snieckus, V. (2018). Directed Remote Lateral Metalation: Highly Substituted 2-Naphthols and BINOLs by In Situ Generation of a Directing Group. Angewandte Chemie International Edition, 57(30), 9425-9429. https://doi.org/10.1002/anie.201805203

• Journal Article Type: Article
• Acceptance Date: May 3, 2018
• Online Publication Date: Jun 21, 2018
• Publication Date: 2018-07
• Deposit Date: Aug 8, 2018
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 57
• Issue: 30
• Pages: 9425-9429
• DOI: https://doi.org/10.1002/anie.201805203
• Public URL: https://durham-repository.worktribe.com/output/1324155