Anodic Functionalisation of Alkenes Catalysed by Diselenids

该项目旨在开发一种电化学驱动和硒催化的非活性烯烃氟化和胺化的合成方法，并将其应用于天然产物的合成。碳骨架的氟化反应在药物、抗癌药物或农用化学品的合成中起着至关重要的作用。这类试剂中的氟原子可以I.A.增加代谢稳定性和生物利用度，改变蛋白质-配体相互作用，或可用于药物靶向。尤其是由于这些原因，人们对能够方便地构建含氟化合物的高效方案有着巨大的需求。除了氟化反应外，胺化反应在有机合成中也起着重要的作用，因为C-N键是有机化合物中最突出的结构基元之一。碳-氮键与各种科学学科相关，如生物学(如多肽和蛋白质)、药剂学(如药物设计)或材料科学(如聚酰胺纤维和组织)。在此背景下，为组装C−N键制定高效和可持续的议定书的持续需求变得非常明显。为了特别解决原子和氧化还原经济性的问题，本研究的目的是将二硒化物催化的阳极氧化烯烃作为构建C-F和C-N键的关键步骤。通过避免使用常规的化学氧化剂以及用于结合氟和氮残留物的预氧化构建块(例如，通过亲核取代)，这里提出的概念代表了大多数并行方法的可持续替代方案。此外，可以用多种方法利用电化学在温和的条件下产生和分析活性物种，这一方面可以导致更高的化学选择性，另一方面可以改善对所述反应的机理理解。

The project aims to develop a synthetic method for the electrochemically driven and selenium-catalyzed fluorination and amination of non-activated alkenes and its application in natural product synthesis. Fluorination reactions of carbon skeletons play a crucial role for example in the synthesis of pharmaceuticals, theranostics or agrochemicals. Fluorine atoms in such agents may i.a. increase the metabolic stability and bioavailability, modify protein-ligand interactions, or can be harnessed in drug-targeting. Not least because of these reasons, there is an immense demand for efficient protocols that allow for the facile construction of fluorinated compounds. In addition to fluorinations, also amination reactions play a fundamental role in organic synthesis, as the C–N bond is one of the most prominent structural motifs found in organic compounds. Carbon–nitrogen bonds are of relevance to various scientific disciplines such as biology (e.g., peptide and proteins), pharmaceutics (e.g., drug design), or material sciences (e.g., polyamide fibres and tissues). Against this backdrop, the continuing demand for the development of efficient and sustainable protocols for the assembly of C−N bonds becomes strikingly apparent. To particularly address the issues of atom and redox-economy, the goal of this research is the anodic oxidation alkenes catalysed by diselenides as a key step for the construction of C–F and C–N bonds. By avoiding the use of customary chemical oxidants as well as pre-oxidized building blocks for the incorporation of fluorine and nitrogen residues (e.g., via nucleophilic substitution), the concept proposed herein represents a sustainable alternative to most of concurrent methods. Furthermore, electrochemistry can be exploited in versatile methods to generate and analyse reactive species under mild conditions, which can lead on the hand to higher chemoselectivities and on the other hand to an improved mechanistic understanding of the reactions in question.