Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N−H Insertion Reaction of Metallocarbenes with β-Aminoketone Derivatives

Nicolle, Simon M.; Lewis, William; Hayes, Christopher J.; Moody, Christopher J.

Abstract

A highly stereoselective route to functionalized pyrrolidines from the metal catalyzed diverted N-H insertion of a range of diazocarbonyl compounds with β-aminoketone derivatives is described. A number of catalysts (rhodium(II) carboxylate dimers, copper(I) triflate and an iron(III)porphyrin) are shown to promote the process under mild conditions to give a wide range of highly substituted proline derivatives. The reaction starts with a metallocarbene N-H insertion but is diverted by an intermolecular aldol reaction.

Citation

Nicolle, S. M., Lewis, W., Hayes, C. J., & Moody, C. J. (2016). Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N−H Insertion Reaction of Metallocarbenes with β-Aminoketone Derivatives. Angewandte Chemie International Edition, 55(11), 3749-3753. https://doi.org/10.1002/anie.201511433

• Journal Article Type: Article
• Acceptance Date: Jan 19, 2016
• Online Publication Date: Feb 5, 2016
• Publication Date: Mar 7, 2016
• Deposit Date: Jul 14, 2016
• Publicly Available Date: Jul 14, 2016
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 55
• Issue: 11
• Pages: 3749-3753
• DOI: https://doi.org/10.1002/anie.201511433
• Keywords: Aldol reaction; carbenes; diazo compounds; nitrogen heterocycles; transition-metal catalysis
• Public URL: https://nottingham-repository.worktribe.com/output/781243
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/anie.201511433/abstract
• Additional Information: This is the peer reviewed version of the following article: S. M. Nicolle, W. Lewis, C. J. Hayes, C. J. Moody. Stereoselective synthesis of functionalized pyrrolidines by the diverted NH insertion reaction of metallocarbenes with ß-aminoketone derivatives. Angew. Chem. Int. Ed. 2016, 55, 3749-2753, doi:10.1002/anie.201511433, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/anie.201511433/abstract. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving
• Contract Date: Jul 14, 2016