External Electrolyte‐Free Electrochemical Chloroalkyloxylation of 1,3‐Enynes to Access Chloroalkoxy‐Propargyl Derivatives

A highly efficient electrochemical 1‐chloro‐2‐ethoxylation of 1,3‐enynes using organic chloride salts as chloride sources has been developed under mild conditions without an additional supporting electrolyte. This protocol provides an efficient approach to a series of chloroalkoxy‐propargyl derivatives bearing various functional groups in moderate to high yields. Mechanistic studies revealed that the electro‐oxidative radical addition to the double bond is responsible for the high chemo‐ and regioselectivity observed in this transformation.