Ni-Catalyzed Carboxylation of Aziridines en Route to ß-Amino Acids.

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 ß-amino acids, important building blocks with considerable potential as peptidomimetics.

Base-Promoted C-C Bond Activation Enables Radical Allylation with Homoallylic Alcohols.

The Cα-Cß 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. C-radical addition to the double bond of the title reagents and subsequent base-promoted homolytic Cα-Cß 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.