The Mn-catalyzed paired electrochemical facile oxychlorination of styrenes via the oxygen reduction reaction

Abstract

Reported herein is the electrochemical engendering of chlorine radicals by a manganese catalyst with a controllable pattern, and inexpensive MgCl2 as the chlorine source.

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

“…As reported by Tian et al, in the absence of other radical sources, manganese can catalyze the direct addition of chlorine radicals to the double bond under electrolysis. 121 The reaction occurs upon the anodic formation of the persistent Mn(III)-Cl radical metal complex. As the authors carried out electrolysis in the presence of oxygen, the latter was reduced to superoxide radical and underwent homocoupling with the benzyl radical and decomposition to benzyl alcohol.…”

Transition metal-catalyzed organic reactions in undivided electrochemical cells

“…In 2019, Chen and co-workers reported a manganese-catalyzed electrochemical oxychlorination of styrenes via paired electrolysis. 34 Jiao and co-workers developed a nickel-catalyzed oxygenation of sulfides with water using paired electrolysis. 35 Shimakoshi and co-workers reported an interesting one-pot synthesis of tertiary amides from organic trichlorides using a B 12 derivative as the catalyst by paired electrolysis.…”

Reaching the Full Potential of Electroorganic Synthesis by Paired Electrolysis

“…The synergetic application of transition metal catalysis and electrochemistry has recently emerged as a powerful synthetic strategy for the development of radical‐based transformations [33] . In the context of paired electrolysis, Chen and co‐workers recently reported a Mn‐catalyzed paired electrochemical oxychlorination of styrenes 43 for the synthesis of chloroacetophenones 44 (Figure 16A) [34] . Taking advantage of the ability of electrochemical Mn‐mediated chlorine atom transfer onto alkene for generating carbon‐centered radical 45 [35] and the cathodic oxygen reduction reaction to produce O 2 radical anion 46 as persistent radical species, the radical‐radical cross coupling was proposed to yield intermediate 47 .…”