Szkop Kevin M, Geeson Michael B, Stephan Douglas W, Cummins Christopher C
Department of Chemistry , University of Toronto , 80 St George St , Toronto , Ontario M5S3H6 , Canada . Email:
Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , MA 02139-4307 , USA . Email:
Chem Sci. 2019 Feb 7;10(12):3627-3631. doi: 10.1039/c8sc05657a. eCollection 2019 Mar 28.
Acyl(chloro)phosphines RC(O)P(Cl)(-Bu) have been prepared by formal insertion of -butyl phosphinidene (-Bu-P) from -BuP ( = CH 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.
通过将来自(-BuP)（( = CH)或蒽）的(-丁基磷烯（(-Bu-P)）正式插入酰氯的(C-Cl)键中，制备了酰基（氯）膦(RC(O)P(Cl)(-Bu))。我们表明，尚未充分探索的酰基（氯）膦官能团提供了一种制备双（酰基）膦的有效方法，双（酰基）膦是工业上用作自由基聚合引发剂的化合物的重要前体。对我们合成方法制备酰基（氯）膦的机理进行的实验和计算研究揭示了一条途径，其中氯离子攻击鏻中间体，并导致在从(P(v))到(P(iii))的过程中磷中心的蒽发生还原损失。酰基（氯）膦官能团的合成适用性已通过还原为酰基磷阴离子得到证明，该阴离子又可以用酰氯处理以提供不对称双（酰基）膦。
