Phospholenes from Phosphabenzenes by Selective Ring Contraction.

Autor:	Lin J; Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstrasse 34/36, 14195, Berlin, Germany., Coles NT; Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstrasse 34/36, 14195, Berlin, Germany.; School of Chemistry, University of Nottingham University Park, Nottingham, NG7 2RD, UK., Dettling L; Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstrasse 34/36, 14195, Berlin, Germany., Steiner L; Freie Universität Berlin, Institut für Chemie und Biochemie, Arnimallee 22, 14195, Berlin, Germany., Felix Witte J; Freie Universität Berlin, Institut für Chemie und Biochemie, Arnimallee 22, 14195, Berlin, Germany., Paulus B; Freie Universität Berlin, Institut für Chemie und Biochemie, Arnimallee 22, 14195, Berlin, Germany., Müller C; Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstrasse 34/36, 14195, Berlin, Germany.
Jazyk:	angličtina
Zdroj:	Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Dec 27; Vol. 28 (72), pp. e202203406. Date of Electronic Publication: 2022 Dec 08.
DOI:	10.1002/chem.202203406
Abstrakt:	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. (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze:	MEDLINE
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