Redox-neutral organocatalytic Mitsunobu reactions

Beddoe, Rhydian H.; Andrews, Keith G.; Magné, Valentin; Cuthbertson, James D.; Saska, Jan; Shannon-Little, Andrew L.; Shanahan, Stephen E.; Sneddon, Helen F.; Denton, Ross M.

Abstract

The Mitsunobu reaction is widely used to invert the configuration of alcohols. However, its major drawback is the need to activate the alcohol with a full equivalent of phosphine, thereby generating a phosphine oxide co-product. Beddoe et al. report a phosphine oxide compound that achieves the same result catalytically (see the Perspective by Longwitz and Werner). The key is a phenol substituent that can reversibly bond through its oxygen to phosphorus, forming a ring that the alcohol opens. The phosphorus thus remains in the +5 oxidation state throughout the reaction, and water is the only by-product.

Citation

Beddoe, R. H., Andrews, K. G., Magné, V., Cuthbertson, J. D., Saska, J., Shannon-Little, A. L., …Denton, R. M. (2019). Redox-neutral organocatalytic Mitsunobu reactions. Science, 365(6456), 910-914. https://doi.org/10.1126/science.aax3353

• Journal Article Type: Article
• Acceptance Date: Jul 30, 2019
• Online Publication Date: Aug 30, 2019
• Publication Date: Aug 30, 2019
• Deposit Date: May 14, 2024
• Journal: Science
• Print ISSN: 0036-8075
• Electronic ISSN: 1095-9203
• Publisher: American Association for the Advancement of Science
• Peer Reviewed: Peer Reviewed
• Volume: 365
• Issue: 6456
• Pages: 910-914
• DOI: https://doi.org/10.1126/science.aax3353
• Public URL: https://durham-repository.worktribe.com/output/2438854