Herein we reported an additive-free protocol for the facile synthesis of α,α-dichloroketones and α-chlorohydrins from various aryl terminal, diaryl internal, and aliphatic terminal alkynes and alkenes, respectively. The commercialized tert-butyl hypochlorite (tBuOCl) was employed as a suitable chlorinating reagent, being accompanied by the less harmful tBuOH as the by-product. In addition, the oxygen atoms in the products came from water, rather than molecular oxygen based on the 18O-labelling experiments. Meanwhile, the diastereoselectivity of the Z- and the corresponding E-alkenes had been compared and rationalized. By a group of control experiments, the possible mechanisms had been proposed as the initial electrophilic chlorination of unsaturated C-C bonds in a Markovnikov-addition manner in general and the following nucleophilic addition with water. This work simplified the oxychlorination method with a mild chlorine source and a green oxygen source under ambient conditions.

You have access to this article

Please wait while we load your content... Something went wrong. Try again?