A Ni-catalyzed reductive carboxylation of N-substituted aziridines with CO2 at atmospheric pressure is disclosed. The protocol is characterized by its mild conditions, experimental ease, and exquisite chemo- and regioselectivity pattern, thus unlocking a new catalytic blueprint to access β-amino acids, important building blocks with considerable potential as peptidomimetics.

The C α −C β bond in homoallylic alcohols can be activated under basic conditions, qualifying these nonstrained acyclic systems as radical allylation reagents. This reactivity is exemplified by photoinitiated (with visible light and/or blue LEDs) allylation of perfluoroalkyl and alkyl radicals generated from perfluoroalkyl iodides and alkylpyridinium salts, respectively, with homoallylic alcohols. Cradical addition to the double bond of the title reagents and subsequent base-promoted homolytic C α −C β cleavage leads to the formation of the corresponding allylated products along with ketyl radicals that act as single electron reductants to sustain the chain reactions. Substrate scope is documented and the role of base in the C−C bond activation is studied by computation.

Intramolecular atom and group transfers are common steps in radical cascade reactions that have been utilized in various transformations. These types of radical translocations (group shifts) are reported for, but not limited to, alkenyl, alkynyl, aryl, cyano, chalcogenyl, and boryl groups. However, the intramolecular radical transfer of an oxygen atom is barely known. Herein, we disclose a radical transformation that allows intramolecular oxygen atom transfer to alkenes, utilizing the nitro functionality in nitroarenes as an oxygen donor. Reactions proceed via iron-catalyzed metal hydrogen atom transfer to alkenes with subsequent oxygenation resulting in alkene hydration. As compared to the intermolecular radical oxygenation, which is well investigated, the intramolecular variant offers advantages, particularly considering diastereoselective radical hydration of conformationally flexible alkenes. The aryl moiety connecting the reactive NO2-functionality to the alkene substrate can be cleaved after oxygen transfer, yielding products that derive from a formal diastereoselective intermolecular alkene hydration. On the other hand, the aniline entity resulting after oxygen transfer can be used for construction of nitrogen-containing heterocycles.