Sodium Hypochlorite Pentahydrate as a Chlorinating Reagent: Application to the Tandem Conversion of β,γ-Unsaturated Carboxylic Acids to α,β-Unsaturated Lactones

Abstract

Sodium hypochlorite pentahydrate (NaClO·5H2O, 1) has recently been employed in organic synthesis as an oxidant for alcohols, sulfides, glycols, etc. In most of these reactions, however, reagent 1 functions just as a simple oxidant, and the variations of the reactions have not been well explored. In this study, we report another useful and fascinating reaction, in which reagent 1 functions as a green chlorinating reagent toward β,γ-unsaturated carboxylic acid (2). When substrate 2 was stirred at room temperature with 1 (2 eq) in acetonitrile for 1 h, α,β-unsaturated lactone (3) was obtained in moderate yields (up to 62%). The same reaction proceeded in various organic and aqueous solvents as well. When excess reagent 1 was employed, lactone 3 was further oxidized to the corresponding epoxide (4) for some cases. The conversion is initiated by electrophilic attack of HOCl to the C=C bond of 2 to generate a chloronium ion intermediate, which is cyclized to β-chlorolactone (5) and then 3 through the elimination of HCl. The usefulness of 1 as a chlorinating reagent was further demonstrated in the electrophilic substitution of activated aromatic compounds.