posted on 2024-01-04, 22:15authored byBin Zhang, Tian-Tian Li, Zhi-Cheng Mao, Min Jiang, Zhihan Zhang, Ke Zhao, Wen-Yuan Qu, Wen-Jing Xiao, Jia-Rong Chen
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. To overcome these issues,
here, we develop a new redox-neutral strategy that seamlessly merges
photoredox and copper catalysis to enable the controlled generation
of alkene radical anions and their orthogonal enantioselective cyanofunctionalization
via distonic-like species. This new strategy enables highly regio-,
chemo-, and enantioselective hydrocyanation, deuterocyanation, and
cyanocarboxylation of alkenes without stoichiometric reductants or
oxidants under visible light irradiation. This protocol provides a
new blueprint for the exploration of the transformation potential
of alkene radical anions.