The direct amination of aliphatic CÀHb onds has remained one of the most tantalizing transformations in organic chemistry.H erein, we report on au nique catalyst system, which enables the elusive intermolecular C(sp 3 ) À H amination. This practical synthetic strategy provides access to aminated building blocks and fosters innovative multiple CÀH amination within an ew approach to aminated heterocycles. The synthetic utility is demonstrated by the synthesis of four relevant pharmaceuticals. Prof. Dr.K.MuÇiz ICREA Pg. LluísC ompanys 23, 08010 Barcelona (Spain) Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

A photochemical catalytic amination of arenes is presented. The reaction proceeds under benign iodine catalysis in the presence of visible light as the initiator and provides access to a range of differently substituted arylamines. A total of 29 examples demonstrate the broad applicability of this mild oxidation method. The scope of the reaction could further be expanded to silyl-tethered derivatives, which undergo intramolecular amination upon formation of seven-membered heterocycles. Cleavage of the silicon tether provides access to the corresponding 3-substituted anilines.

The catalytic Hofmann–Löffler reaction represents a uniquely effective protocol for the formation of pharmaceutically relevant heterocycles and is based on the reactivity of N‐halogenated amines. Herein, we report stoichiometric experimentation toward the detection of a sulfonamidyl radical as the decisive intermediate in this C‐H amination reaction. It can be observed by EPR after homolytic cleavage of the in situ formed N‐halogen bond under the conditions of the iodine or bromine catalyzed Hofmann–Löffler reaction.

An innovative approach to position-selective polyhalogenation of aliphatic hydrocarbon bonds is presented. The reaction proceeded within the Hofmann-Löffler manifold with amidyl radicals as the sole mediators to induce selective 1,5- and 1,6-hydrogen-atom transfer followed by halogenation. Multiple halogenation events of up to four innate C-H bond functionalizations were accomplished. The broad applicability of this new entry into polyhalogenation and the resulting synthetic possibilities were demonstrated for a total of 27 different examples including mixed halogenations.

In contrast to aryliodine(III) compounds, which have matured into a particularly attractive class of oxidants in modern synthesis, the synthetic potential of related alkyliodine(III) derivatives has remained widely underestimated. This is surprising since several unique synthetic possibilities arise directly from the low stability of their central carbon–iodine bond. In this respect, these high‐oxidation‐state iodine compounds resemble environmentally benign variants of the prominent metal counterparts such as those derived from palladium, nickel and copper. This Concept article summarizes the general reactivity trends in alkyliodine(III) chemistry and discusses selected examples of their strategic use as highly reactive, transient species in organic synthesis and homogeneous catalysis.

NTs 2

A cyclic β-dicarbonyl phenyliodonium ylide reacted with various substituted styrenes under Rh2(OAc)4 catalysis to give cyclopropanes and dihydrofurans in a highly regioselective fashion. When styrenes with electron-donating substituents or disubstituted were employed, only dihydrofurans were isolated instead. A mechanism involving two competing pathways rationalizes the results.

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