Exploiting the Brønsted Acidity of Phosphinecarboxamides for the Synthesis of New Phosphides and Phosphines. Issue 22 (17th April 2015)

• Record Type: Journal Article
• Authors: Jupp, Andrew R.; Trott, Gemma; Payen de la Garanderie, Éléonore; Holl, James D. G.; Carmichael, Duncan; Goicoechea, Jose M.
• Is Part Of: Chemistry. Volume 21:Issue 22(2015)
• Page Start: 8015
• Page End: 8018
• Publication Date: 2015-04-17
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201501174
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>We demonstrate that the synthesis of new <italic>N</italic>‐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 <italic>N</italic>‐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.</p> </abstract>