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Rational design of Fe catalysts for olefin aziridination through DFT-based mechanistic analysis
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2017-09-12 00:00:00 , DOI: 10.1039/c7cy01283g Ranjan Patra 1, 2, 3, 4, 5 , Guillaume Coin 1, 2, 3, 4, 5 , Ludovic Castro 1, 2, 3, 6, 7 , Patrick Dubourdeaux 1, 2, 3, 4, 5 , Martin Clémancey 1, 2, 3, 4, 5 , Jacques Pécaut 1, 2, 3, 6, 7 , Colette Lebrun 1, 2, 3, 6, 7 , Pascale Maldivi 1, 2, 3, 6, 7 , Jean-Marc Latour 1, 2, 3, 4, 5
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2017-09-12 00:00:00 , DOI: 10.1039/c7cy01283g Ranjan Patra 1, 2, 3, 4, 5 , Guillaume Coin 1, 2, 3, 4, 5 , Ludovic Castro 1, 2, 3, 6, 7 , Patrick Dubourdeaux 1, 2, 3, 4, 5 , Martin Clémancey 1, 2, 3, 4, 5 , Jacques Pécaut 1, 2, 3, 6, 7 , Colette Lebrun 1, 2, 3, 6, 7 , Pascale Maldivi 1, 2, 3, 6, 7 , Jean-Marc Latour 1, 2, 3, 4, 5
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Nitrene transfer reactions are increasingly used to access various kinds of amine derivatives but the underlying mechanisms have not been unraveled in most cases. Fe-catalyzed aziridination of alkenes has appeared as a promising route to aziridines which are important derivatives both per se and as intermediates in many synthetic procedures. We report the strong activity and the mechanism of di-iron catalysts for aziridination of styrenes using phenyltosyliodinane (PhI![[double bond, length as m-dash]](http://www.rsc.org/images/entities/char_e001.gif)
NTs). In addition, we have developed a similar mono-iron catalyst which operates under the same mechanism albeit with a reduced activity. DFT calculations were performed to investigate the structure and electronic structure of the FeIVNTs species of the latter catalyst. They suggest that the reaction pathway leading to the nitrene transfer to the olefin involves a transient charge transfer on the way to a radical intermediate, which is totally consistent with the experimental results. Moreover, these calculations identify the electron affinity (EA) of the active species as one key parameter allowing rationalization of the observations, which opens the way to improving the catalyst efficiency on a rational basis.
中文翻译：
基于DFT的机械分析合理设计烯烃叠氮化铁催化剂。
丁二烯转移反应越来越多地用于获取各种胺衍生物，但在大多数情况下尚未阐明其潜在机理。铁催化的烯烃的叠氮化已显示出是制备氮丙啶的有前途的途径，其本身是重要的衍生物，并且在许多合成方法中作为中间体。我们报道了使用苯基甲苯磺酰亚胺（PhI NTs）的苯乙烯的叠氮化二铁催化剂的强活性和机理。此外，我们已经开发出了一种类似的单铁催化剂，尽管其活性降低了，但仍在相同的机理下运行。进行了DFT计算以研究Fe IV的结构和电子结构后一种催化剂的NTs种。他们认为导致腈转移到烯烃的反应途径涉及到自由基中间体的瞬时电荷转移，这与实验结果完全一致。此外，这些计算将活性物质的电子亲和力（EA）确定为一个关键参数，可以使观察值合理化，这为合理提高催化剂效率开辟了道路。
更新日期：2017-09-12
NTs). In addition, we have developed a similar mono-iron catalyst which operates under the same mechanism albeit with a reduced activity. DFT calculations were performed to investigate the structure and electronic structure of the FeIVNTs species of the latter catalyst. They suggest that the reaction pathway leading to the nitrene transfer to the olefin involves a transient charge transfer on the way to a radical intermediate, which is totally consistent with the experimental results. Moreover, these calculations identify the electron affinity (EA) of the active species as one key parameter allowing rationalization of the observations, which opens the way to improving the catalyst efficiency on a rational basis.
中文翻译：
基于DFT的机械分析合理设计烯烃叠氮化铁催化剂。
丁二烯转移反应越来越多地用于获取各种胺衍生物，但在大多数情况下尚未阐明其潜在机理。铁催化的烯烃的叠氮化已显示出是制备氮丙啶的有前途的途径，其本身是重要的衍生物，并且在许多合成方法中作为中间体。我们报道了使用苯基甲苯磺
酰亚胺（PhI NTs）的苯乙烯的叠氮化二铁催化剂的强活性和机理。此外，我们已经开发出了一种类似的单铁催化剂，尽管其活性降低了，但仍在相同的机理下运行。进行了DFT计算以研究Fe IV的结构和电子结构后一种催化剂的NTs种。他们认为导致腈转移到烯烃的反应途径涉及到自由基中间体的瞬时电荷转移，这与实验结果完全一致。此外，这些计算将活性物质的电子亲和力（EA）确定为一个关键参数，可以使观察值合理化，这为合理提高催化剂效率开辟了道路。
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