Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer
Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer
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DOI：
10.1039/c8sc05657a
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发表时间：
2019-03-28
期刊：
影响因子：
8.4
通讯作者：
Cummins, Christopher C.
中科院分区：
文献类型：
--
作者：
Szkop, Kevin M.;Geeson, Michael B.;Cummins, Christopher C.
以叔丁基膦（t-BuPA）（A = C14 H10或蒽）为原料，将叔丁基次膦（t-Bu-P）插入到酰氯的C-Cl键上，合成了酰基（氯）膦RC（O）P（Cl）（t-Bu）。我们发现，未开发的酰基（氯）膦官能团提供了一种有效的方法来制备双（酰基）膦，这是重要的前体化合物在工业上用作自由基聚合引发剂。通过我们的合成方法形成酰基（氯）膦的机制的实验和计算研究揭示了一种途径，其中氯化物攻击磷中间体，并导致从磷中心的P（V）到P（III）过程中的蒽的还原损失。酰基（氯）膦官能团的合成适用性已通过还原成酰基磷阴离子而得到证明，酰基磷阴离子又可以用酰氯处理以提供不对称的双（酰基）膦。
Acyl(chloro)phosphines RC(O)P(Cl)(t-Bu) have been prepared by formal insertion of tert-butyl phosphinidene (t-Bu-P) from t-BuPA (A = C14H10 or anthracene) into the C-Cl bond of acyl chlorides. We show that the under-explored acyl(chloro)phosphine functional group provides an efficient method to prepare bis(acyl)phosphines, which are important precursors to compounds used industrially as radical polymerization initiators. Experimental and computational investigations into the mechanism of formation of acyl(chloro)phosphines by our synthetic method reveal a pathway in which chloride attacks a phosphonium intermediate and leads to the reductive loss of anthracene from the phosphorus center in a P(v) to P(iii) process. The synthetic applicability of the acyl(chloro)phosphine functional group has been demonstrated by reduction to an acylphosphide anion, which can in turn be treated with an acyl chloride to furnish dissymmetric bis(acyl)phosphines.