Ferrous ion induced decomposition of alkyl hypochlorites

The decomposition of primary, secondary and tertiary alkyl hypochlorites induced by ferrous and other one-electron oxidizable metal ions leads to δ-chloro alcohols in yields of 34–76%. In decomposition of tertiary alkyl hypochlorites, β-fragmentation competes with intramolecular δ-chlorination. Tertiary cycloalkyl hypochlorites containing five- or six-membered rings undergo β-cleavage giving the corresponding ω-chloro ketones, while 1-methylcycloheptyl and 1-methylcyclooctyl hypochlorites by decomposition with ferrous ion proceed by transannular functionalization of δ-carbon atom and β-cleavage as a competing reaction.