Exploiting the Brønsted acidity of phosphinecarboxamides for the synthesis of new phosphides and phosphines.
Exploiting the Brønsted acidity of phosphinecarboxamides for the synthesis of new phosphides and phosphines.
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DOI：
10.1002/chem.201501174
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发表时间：
2015-05-26
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影响因子：
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通讯作者：
Goicoechea JM
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文献类型：
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作者：
Jupp AR;Trott G;Payen de la Garanderie É;Holl JD;Carmichael D;Goicoechea JM
我们证明，新的N-官能化膦酰胺的合成是可能的，通过反应的伯胺和仲胺与PCO−在质子源的存在下。这些反应以不同程度的成功进行，并且尽管伯胺通常以良好的产率提供相应的膦甲酰胺，仲胺反应更缓慢并且通常引起2-磷炔酸酯前体的显著分解。在现有的新的N-衍生化膦酰胺中，PH 2C（O）NHCy（Cy=环己基）可以以足够高的产率获得，以允许探索其布朗斯台德酸度。因此，用一当量的二（三甲基硅基）氨基钾（KHMDS）使PH 2C（O）NHCy去质子化，得到新的磷化物[PHC（O）NHCy]−。相反，用一半当量去质子化产生[P{C（O）NHCy}2]−和PH 3。这些磷化物可以通过与亲电试剂反应得到新的膦，从而展示了它们作为化学结构单元的巨大潜力。
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.