Electrochemical Atom Transfer Radical Addition of Polychloroalkanes to Olefins Promoted by 4,4-Di-tert-butyl Bipyridine

A new electrochemical strategy for the atom transfer radical addition (ATRA) of polychloroalkanes across olefins has been realized by the synergism of paired electrolysis and halogen bonding activation. Notably, readily accessible 4,4-di-tert-butyl bipyridine (dtbpy), acting as a halogen bonding acceptor, shifted the reduction potential of C-Cl bonds positively by 110 mV. The decreased operating potential leads to a wide substrate scope and excellent functional group compatibility. A diverse array of terminal and internal alkenes such as (hetero)aryl olefins, unactive aliphatic olefins, and natural products and drugs-derived olefins were well compatible.

Automated summary

A new electrochemical strategy utilizing paired electrolysis and halogen bonding activation has been developed for the atom transfer radical addition (ATRA) of polychloroalkanes across olefins. By employing readily accessible 4,4-di-tert-butyl bipyridine (dtbpy) as a halogen bonding acceptor, the reduction potential of C-Cl bonds could be positively shifted by 110 mV. This approach allows for a wide substrate scope and excellent functional group compatibility, enabling the addition of various terminal and internal alkenes.