Andries-Ulmer Anna, Brunner Christoph, Rehbein Julia, Gulder Tanja
Department of Chemistry and Catalysis Research Center (CRC) , Technical University of Munich , Lichtenbergstraße 4 , 85748 Garching , Germany.
Institute of Organic Chemistry , University of Regensburg , Universitätstraße 31 , 93053 Regensburg , Germany.
J Am Chem Soc. 2018 Oct 10;140(40):13034-13041. doi: 10.1021/jacs.8b08350. Epub 2018 Sep 18.
Despite ample evidence for the unique reactivity offered by hypervalent F-iodanes, mechanistic investigations fall far behind. In order to shed light on the unusual behavior of such F-reagents, we conducted computational and experimental studies on the chemodivergent transformation of styrenes. We identified the spirocyclic F-cyclopropane as the common intermediate for both the C, H-fluorination and C, H-amination pathways. The fate of this key compound is determined by the extent of cationic charge delocalization controlled by the N-substituents. Exploiting this phenomenon, a multitude of different transformations have become available, leading, i.e., to the regiodivergent synthesis of indoles and tryptophans.
尽管有充分证据表明高价氟代碘烷具有独特的反应活性，但机理研究却远远落后。为了阐明此类含氟试剂的异常行为，我们对苯乙烯的化学发散转化进行了计算和实验研究。我们确定螺环氟代环丙烷是碳氢氟化和碳氢胺化途径的共同中间体。这种关键化合物的命运取决于由氮取代基控制的阳离子电荷离域程度。利用这一现象，已经实现了多种不同的转化，例如导向吲哚和色氨酸的区域发散合成。
