Phospholenes from Phosphabenzenes by Selective Ring Contraction

Lin, Jinxiong; Coles, Nathan T.; Dettling, Lea; Steiner, Luca; Witte, Jan Felix; Paulus, Beate; Müller, Christian

Abstract

A 3-amino-functionalized phosphabenzene (phosphinine) has been synthesized and structurally characterized. The pyramidalized nitrogen atom of the dimethylamino substituent indicates only a weak interaction between the lone pair of the nitrogen atom and the aromatic phosphorus heterocycle, resulting in somewhat basic character. It turned out that the amino group can indeed be protonated by HCl. In contrast to pyridines, however, the phosphabenzene-ammonium salt undergoes a selective ring contraction to form a hydroxylphospholene oxide in the presence of additional water. Based on deuterium labeling experiments and quantum chemical calculations, a rational mechanism for this hitherto unknown conversion is proposed.

Citation

Lin, J., Coles, N. T., Dettling, L., Steiner, L., Witte, J. F., Paulus, B., & Müller, C. (2022). Phospholenes from Phosphabenzenes by Selective Ring Contraction. Chemistry - A European Journal, 28(72), Article e202203406. https://doi.org/10.1002/chem.202203406

• Journal Article Type: Article
• Acceptance Date: Nov 16, 2022
• Online Publication Date: Nov 16, 2022
• Publication Date: Dec 27, 2022
• Deposit Date: Dec 20, 2022
• Publicly Available Date: Dec 20, 2022
• Journal: Chemistry – A European Journal
• Print ISSN: 0947-6539
• Electronic ISSN: 1521-3765
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 28
• Issue: 72
• Article Number: e202203406
• DOI: https://doi.org/10.1002/chem.202203406
• Keywords: General Chemistry, Catalysis, Organic Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/14304688
• Publisher URL: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202203406