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

Andrew R. Jupp, Gemma Trott, Éléonore Payen de la Garanderie, James D. G. Holl, Duncan Carmichael, Jose M. Goicoechea

Research output: Contribution to journalArticlepeer-review

30 Citations (Scopus)
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Abstract

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.
Original languageEnglish
Pages (from-to)8015-8018
Number of pages4
JournalChemistry - A European Journal
Volume21
Issue number22
Early online date17 Apr 2015
DOIs
Publication statusPublished - 26 May 2015

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