A Catalyst‐Free, Transition‐Metal‐Free, and Selective Chloro‐Alkoxylation of Olefins with Alcohols and <i>tert</i> ‐Butyl Hypochlorite

Abstract The development of catalyst‐ and metal‐free methods for vicinal chloro‐functionalization of olefins could provide a highly desirable approach to value‐added organic halides. In this study, the chloro‐alkoxylation of alkenes was achieved at room temperature by using tert ‐butyl hypochlorite ( t BuOCl) as the electrophilic chlorination reagent and alcohols as the nucleophiles. This reaction system could cover a wide range of substrates that aromatic and aliphatic terminal, aromatic and aliphatic internal alkenes were transformed into the corresponding β‐chloroethyl ether products with good yield and regioselectivity, probably following the Markovnikov addition process. In addition, the reaction of α,β‐unsaturated ketone, ester, and acids that were less studied before could afford the major anti‐products in good diastereoselectivity and high yields. Furthermore, this method could be applied to the late‐stage functionalization of complex substrates bearing naturally occurring scaffolds. This work established a simple, atom‐economic, easy‐handling, and synthetic valuable protocol for the transformation of bulk chemicals like olefins and alcohols to access various β‐chloroethyl ethers, including 30 new compounds with a preferred chlorination reagent.