Mechanism of the phospha-Wittig-Horner reaction.
Mechanism of the phospha-Wittig-Horner reaction.
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DOI：
10.1002/anie.201301469
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发表时间：
2013-06-17
影响因子：
16.6
通讯作者：
Ott, Sascha
中科院分区：
文献类型：
--
作者：
Arkhypchuk, Anna I.;Svyaschenko, Yurii V.;Orthaber, Andreas;Ott, Sascha
由于其π-受体能力[1]，磷杂烯烃在均相催化中是突出的配体，并且是聚合物科学中有吸引力的结构单元。[1b然而，它们的制备方法通常受到小的底物范围或源自某些合成方法的残留OTMS取代基的限制。[3]磷脂-维蒂希-霍纳（pWH）反应，首先由Mathey和同事发明[4]，将醛和相对不活泼的酮分别转化为C-单和C，C-二取代的磷脂烯（方案1，顶部）。此外，在磷中心的取代基可以相当自由地选择，尽管较小的基团需要通过金属配位的额外稳定。[5]在我们之前关于将低价磷掺入不饱和碳支架的工作的背景下，[6]我们有兴趣看看pWH反应的范围是否可以扩展到烯酮底物，从中可以获得1-磷丙二烯。这种磷杂丙二烯是一类有趣的磷杂丙二烯中最短的成员。
Phosphaalkenes are prominent ligands in homogenous catalysis due to their π-acceptor capacity [1] and are appealing building blocks in polymer science.[1b, 2] Methods for their preparation are however often limited by small substrate scopes, or residual OTMS substituents that stem from certain synthetic methods.[3] The phospha-Wittig–Horner (pWH) reaction, as first coined by Mathey and co-workers,[4] converts aldehydes and relatively unreactive ketones into C-monoand C, C-disubstituted phosphaalkenes, respectively (Scheme 1, top). Furthermore, the substituent at the phosphorus center can be chosen rather freely, although smaller groups demand additional stabilization by metal coordination.[5] In context of our previous work on the incorporation of low-valent phosphorus into unsaturated carbon scaffolds,[6] we were interested to see whether the scope of the pWH reaction could be extended to ketene substrates from which 1-phosphapropadienes would become accessible. Such phosphaallenes are the shortest members of an intriguing class of
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