Design and Scalable Synthesis of N-Alkylhydroxylamine Reagents for the Direct Iron-Catalyzed Installation of Medicinally Relevant Amines**

Secondary and tertiary alkylamines are privileged substance classes that are often found in pharmaceuticals and other biologically active small molecules. Herein, we report their direct synthesis from alkenes through an aminative difunctionalization reaction enabled by iron catalysis. A family of ten novel hydroxylamine-derived aminating reagents were designed for the installation of several medicinally relevant amine groups, such as methylamine, morpholine and piperazine, through the aminochlorination of alkenes. The method has excellent functional group tolerance and a broad scope of alkenes was converted to the corresponding products, including several drug-like molecules. Besides aminochlorination, the installation of other functionalities through aminoazidation, aminohydroxylation and even intramolecular carboamination reactions, was demonstrated, further highlighting the broad potential of these new reagents for the discovery of novel amination reactions.     

Template-Controlled Synthesis of Polyimidazolium Salts by Multiple [2+2] Cycloaddition Reactions

The tetrakisimidazolium salt H₄- 2 (Br)₄, featuring a central benzene linker and 1,2,4,5-(nBu-imidazolium-Ph-CH=CH-) substituents reacts with Ag₂O in the presence of AgBF₄ to yield the tetranuclear, oktakis-NHC assembly [ 3 ](BF₄)₄. Cation [ 3 ]⁴⁺ features four pairs of olefins from the two tetrakis-NHC ligands perfectly arranged for a subsequent [2+2] cycloaddition. Irradiation of [ 3 ](BF₄)₄ with a high pressure Hg lamp connects the two tetra-NHC ligands through four cyclobutane linkers to give compound [ 4 ](BF₄)₄. Removal of the template metals yields the novel oktakisimidazolium salt H₈- 5 (BF₄)₈. The tetrakisimidazolium salt H₄- 2 (BF₄)₄ and the oktakisimidazolium salt H₈- 5 (BF₄)₈ have been used as multivalent anion receptors and their anion binding properties towards six different anions have been compared.     

Electrophotocatalytic SNAr Reactions of Unactivated Aryl Fluorides at Ambient Temperature and Without Base

The electrophotocatalytic S_NAr reaction of unactivated aryl fluorides at ambient temperature without strong base is demonstrated.