Effects of Phosphorus Substituents on Reactions of α-Alkoxyphosphonium Salts with Nucleophiles
作者:Akihiro Goto、Kazuki Otake、Ozora Kubo、Yoshinari Sawama、Tomohiro Maegawa、Hiromichi Fujioka
DOI:10.1002/chem.201200480
日期:2012.9.3
The effects of phosphorus substituents on the reactivity of α‐alkoxyphosphonium salts with nucleophiles has been explored. Reactions of α‐alkoxyphosphonium salts, prepared from various acetals and tris(o‐tolyl)phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high‐yielding nucleophilic substitution reactions of α‐alkoxyphosphonium salts
研究了磷取代基对α-烷氧基salts盐与亲核试剂反应性的影响。由各种缩醛和三(邻甲苯基)膦制备的α-烷氧基phosph盐与各种亲核试剂的反应有效进行。这些过程代表了α-烷氧基phosph盐高亲核取代反应的第一个例子。这些盐的反应性分别取决于空间和电子因素之间的平衡,分别由锥角θ和CO拉伸频率ν(分别为空间和电子参数)表示。此外,由Ph 3衍生的α-烷氧基phosph盐的新反应观察到带有格氏试剂的P在O 2的存在下发生,以高收率得到醇。为此过程提出了一种自由基机理,该机理已获得同位素标记和自由基抑制实验的支持。