Markovnikov versus anti-Markovnikov Hydrophosphination: Divergent Reactivity Using an Iron(II) β-Diketiminate Pre-Catalyst,Chemistry - A European Journal

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Markovnikov versus anti-Markovnikov Hydrophosphination: Divergent Reactivity Using an Iron(II) β-Diketiminate Pre-Catalyst
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2017-06-19 08:20:44 , DOI: 10.1002/chem.201702374
Andrew K. King ₁ , Kimberley J. Gallagher ₁ , Mary F. Mahon ₁ , Ruth L. Webster ₁

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The ability to tune between different regioselectivities using a common pre-catalyst is an unusual yet highly desirable process. Here, we report the use of an iron(II) pre-catalyst that can be used to synthesize vinyl phosphines in a Markovnikov-selective manner in benzene, whereas a simple change to dichloromethane as the reaction solvent leads to the Z-selective anti-Markovnikov product. Preliminary mechanistic studies are reported that suggest Markovnikov selectivity is a radical-mediated process, whereas the anti-Markovnikov selectivity is not radical in nature but is due to a change in oxidation state.

中文翻译：

Markovnikov与抗Markovnikov的加氢磷化反应：使用β-二铁化铁（II）预催化剂的不同反应性

使用普通的预催化剂在不同区域选择性之间进行调节的能力是一个不寻常但非常理想的过程。在这里，我们报告了一种铁（II）预催化剂的使用，该催化剂可用于在苯中以马尔科夫尼科夫选择性方式合成乙烯基膦，而简单地更改为二氯甲烷作为反应溶剂会导致Z选择性反-马尔可夫尼可夫产品。据初步的机理研究表明，马尔可夫尼可夫选择性是自由基介导的过程，而反马尔可夫尼可夫选择性在本质上不是自由基，而是由于氧化态的改变。

更新日期：2017-06-20

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