Exploiting the Brønsted acidity of phosphinecarboxamides for the synthesis of new phosphides and phosphines.

Autor: Jupp AR; Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA (UK)., Trott G; Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA (UK)., Payen de la Garanderie É; Laboratoire de Chimie Moléculaire, École Polytechnique, CNRS, 91128 Palaiseau cedex (France)., Holl JD; Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA (UK)., Carmichael D; Laboratoire de Chimie Moléculaire, École Polytechnique, CNRS, 91128 Palaiseau cedex (France)., Goicoechea JM; Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA (UK). jose.goicoechea@chem.ox.ac.uk.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2015 May 26; Vol. 21 (22), pp. 8015-8. Date of Electronic Publication: 2015 Apr 17.
DOI: 10.1002/chem.201501174
Abstrakt: We demonstrate that the synthesis of new N-functionalized phosphinecarboxamides is possible by reaction of primary and secondary amines with PCO(-) in the presence of a proton source. These reactions proceed with varying degrees of success, and although primary amines generally afford the corresponding phosphinecarboxamides in good yields, secondary amines react more sluggishly and often give rise to significant decomposition of the 2-phosphaethynolate precursor. Of the new N-derivatized phosphinecarboxamides available, PH2C(O)NHCy (Cy = cyclohexyl) can be obtained in sufficiently high yields to allow for the exploration of its Brønsted acidity. Thus, deprotonating PH2C(O)NHCy with one equivalent of potassium bis(trimethylsilyl)amide (KHMDS) gave the new phosphide [PHC(O)NHCy](-). In contrast, deprotonation with half of an equivalent gives rise to [P{C(O)NHCy}2](-) and PH3. These phosphides can be employed to give new phosphines by reactions with electrophiles, thus demonstrating their enormous potential as chemical building blocks.
(© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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