Mechanism (biology)

Catalysis

Philosophy

Selectfluor

Photochemistry

Electrophile

Crossover

Alkyl

Computer science

Alkene

Markovnikov's rule

Medicinal chemistry

Reactive intermediate

Combinatorial chemistry

Physics

Organic chemistry

Carbanion

Reagent

Astronomy

Polar

Epistemology

Radical ion

Computational chemistry

Regioselectivity

Artificial intelligence

Radical

Chemistry

Journal of the American Chemical Society

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated in a variety of alkene functionalization reactions, most of which proceed via an anodic oxidation pathway. In this report, we further expand the scope of electrochemistry to the reductive functionalization of alkenes. In particular, the strategic choice of reagents and reaction conditions enabled a radical-polar crossover pathway wherein two distinct electrophiles can be added across an alkene in a highly chemo- and regioselective fashion. Specifically, we used this strategy in the intermolecular carboformylation, anti-Markovnikov hydroalkylation, and carbocarboxylation of alkenes—reactions with rare precedents in the literature—by means of the electroreductive generation of alkyl radical and carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) and simple, transition-metal-free conditions and display broad substrate scope and good tolerance of functional groups. A uniform protocol can be used to achieve all three transformations by simply altering the reaction medium. This development provides a new avenue for constructing Csp3–Csp3 bonds.

Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism