Hydrophosphination of Unactivated Alkenes and Alkynes Using Iron(II): Catalysis and Mechanistic Insight
Hydrophosphination of Unactivated Alkenes and Alkynes Using Iron(II): Catalysis and Mechanistic Insight
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DOI：
10.1021/acscatal.6b02290
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发表时间：
2016-11-01
期刊：
影响因子：
12.9
通讯作者：
Webster, Ruth L.
中科院分区：
文献类型：
--
作者：
Espinal-Viguri, Maialen;King, Andrew K.;Webster, Ruth L.
膦与烯烃和炔的催化加成是一种非常有吸引力的方法，该方法使用容易获得且廉价的材料以100%原子经济的反应提供膦。这些产物是潜在的有用的配体和有机催化剂。在这里，我们报告的第一个例子，一系列非活化的膦基烯烃和膦基炔与一个简单的铁β-二酮亚胺络合物的分子内氢化膦化。动力学研究表明，这种转化对于磷化氢和催化剂来说都是一级的。铁催化的氢膦化的机理解释，收集的实验证据的支持。
The catalytic addition of phosphines to alkenes and alkynes is a very attractive process that offers access to phosphines in a 100% atom-economic reaction using readily available and inexpensive materials. The products are potentially useful ligands and organocatalysts. Herein, we report the first example of intramolecular hydrophosphination of a series of nonactivated phosphinoalkenes and phosphinoalkynes with a simple iron beta-diketiminate complex. Kinetic studies suggest that this transformation is first-order with respect to both the phosphine and the catalyst. A mechanistic interpretation of the iron-catalyzed hydrophosphination is presented, supported by the experimental evidence collected.