TY - JOUR
T1 - Exploiting the Brønsted acidity of phosphinecarboxamides for the synthesis of new phosphides and phosphines
AU - Jupp, Andrew R.
AU - Trott, Gemma
AU - Payen de la Garanderie, Éléonore
AU - Holl, James D. G.
AU - Carmichael, Duncan
AU - Goicoechea, Jose M.
PY - 2015/5/26
Y1 - 2015/5/26
N2 - 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.
AB - 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.
U2 - 10.1002/chem.201501174
DO - 10.1002/chem.201501174
M3 - Article
SN - 0947-6539
VL - 21
SP - 8015
EP - 8018
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 22
ER -