Iron-catalyzed radical Markovnikov hydrohalogenation and hydroazidation of alkenes.

We herein report radical hydroazidation and hydrohalogenation of mono-, di- and trisubstituted alkenes through iron catalysis. The alkene moiety that often occurs as a functionality in natural products is readily transformed into useful building blocks through this approach. Commercially available tosylates and α-halogenated esters are used as radical trapping reagents in combination with silanes as reductants.

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

A Ni-catalyzed reductive carboxylation of substituted aziridines with CO 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.

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

The C-C 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 C-C 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.