# Chemoselectively Functionalized Ketoesters by Halogenative C–C Bond Cleavage of Cyclic Diketones

## TL;DR

This paper introduces a new method to efficiently and selectively produce haloketoesters from cyclic diketones under mild conditions.

## Contribution

A novel synthetic approach for the selective production of haloketoesters via halogenative C–C bond cleavage is introduced.

## Key findings

- A new method for synthesizing di- and trichloro-functionalized ketoesters from 1,3-cyclohexadiones was developed.
- Na2HPO4 was found to be effective in facilitating the alcoholytic ring-opening reaction of 2,2-dichloro-1,3-cyclohexadiones.
- The method operates under mild conditions and provides a direct route to haloketoesters.

## Abstract

Haloketoesters are synthetic intermediates in various cyclization reactions that facilitate the production of biologically active compounds. Nonetheless, the selective synthesis of dihaloketoesters and trihaloketoesters, which are expected to be highly versatile, presents significant challenges. In this study, we designed a new synthetic approach that selectively and efficiently produces haloketoesters through the halogenative C–C bond cleavage and ring-opening reactions of cyclic 1,3-diketones. This convenient method enables the direct synthesis of di- and trichloro-functionalized ketoesters from 1,3-cyclohexadiones under mild conditions. Na2HPO4, employed as a buffer salt, proved to be effective in facilitating the alcoholytic ring-opening reaction of 2,2-dichloro-1,3-cyclohexadiones, which were generated as synthetic intermediates.