Unlocking Epoxide Radical Anion Reactivity for Asymmetric Cross-Coupling by Copper Metallaphotoredox.

The ability to tame radical anions that feature both an unpaired spin and a charge is critical for synthetic chemistry, enabling the construction of diverse chemical bonds via unique reaction pathways and promoting advances in the area of synthesis. In this regard, C(sp)-rich epoxide radical anions are particularly attractive but often elusive, highly reactive intermediates. Classic methods to access epoxide radical anions exploit single-electron chemistry by using dissolving alkali, sacrificial electrodes, or redox metals.

Enantioselective Cyanofunctionalization of Aromatic Alkenes via Radical Anions.

Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis of valuable compounds because they have both unpaired spins and charge. However, relatively few synthetic applications of alkene radical anions have emerged due to a dearth of generally applicable and mild radical anion generation approaches. Precise control over the chemo- and stereoselectivity in alkene radical anion-mediated processes represents another long-standing challenge due to their high reactivity.