Remote Nucleophilic Allylation by Allylrhodium Chain Walking

Martínez, Jose I.; Groves, Alistair; Martinez, Jose I.; Smith, Joshua J.; Lam, Hon Wai

Abstract

Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and an imine to give Z-homoallylic alcohols and amines, respectively.

Citation

Martínez, J. I., Groves, A., Martinez, J. I., Smith, J. J., & Lam, H. W. (2018). Remote Nucleophilic Allylation by Allylrhodium Chain Walking. Chemistry - A European Journal, 24(51), 13432-13436. https://doi.org/10.1002/chem.201803574

• Journal Article Type: Article
• Acceptance Date: Jul 13, 2018
• Online Publication Date: Jul 13, 2018
• Publication Date: Sep 12, 2018
• Deposit Date: Jul 20, 2018
• Publicly Available Date: Jul 20, 2018
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Electronic ISSN: 1521-3765
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 24
• Issue: 51
• Pages: 13432-13436
• DOI: https://doi.org/10.1002/chem.201803574
• Keywords: allylation, chain walking, homogenous catalysis, isomerization, rhodium
• Public URL: https://nottingham-repository.worktribe.com/output/946308
• Publisher URL: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201803574
• Additional Information: This is the peer reviewed version of the following article, which has been published in final form at https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201803574. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
• Contract Date: Jul 20, 2018