Iron(II)-Catalyzed Hydrophosphination of Isocyanates

Sharpe, Helen R.; Geer, Ana M.; Lewis, William; Blake, Alexander J.; Kays, Deborah L.

Abstract

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The first transition metal catalyzed hydrophosphination of isocyanates is presented. The use of low-coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P−H bond of diphenylphosphine to yield phosphinodicarboxamides [Ph2PC(=O)N(R)C(=O)N(H)R], a new family of derivatized organophosphorus compounds. This remarkable result can be attributed to the low-coordinate nature of the iron(II) centers whose inherent electron deficiency enables a Lewis-acid mechanism in which a combination of the steric pocket of the metal center and substrate size determines the reaction products and regioselectivity.

Citation

Sharpe, H. R., Geer, A. M., Lewis, W., Blake, A. J., & Kays, D. L. (2017). Iron(II)-Catalyzed Hydrophosphination of Isocyanates. Angewandte Chemie International Edition, 56(17), 4845-4848. https://doi.org/10.1002/anie.201701051

• Journal Article Type: Article
• Acceptance Date: Mar 2, 2017
• Online Publication Date: Mar 24, 2017
• Publication Date: Apr 18, 2017
• Deposit Date: Apr 4, 2017
• Publicly Available Date: Apr 4, 2017
• Journal: Angewandte Chemie - International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 56
• Issue: 17
• Pages: 4845-4848
• DOI: https://doi.org/10.1002/anie.201701051
• Keywords: Hydrophosphination, Iron, Isocyanates, m-terphenyl ligands, Homogeneous catalysis
• Public URL: https://nottingham-repository.worktribe.com/output/856355
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/anie.201701051/abstract
• Additional Information: This is the peer reviewed version of the following article: H. R. Sharpe, A. M. Geer, W. Lewis, A. J. Blake, D. L. Kays, Angew. Chem. Int. Ed. 2017, 56, 4845. doi:10.1002/anie.201701051, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/anie.201701051/abstract. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.