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Additive-free oxychlorination of unsaturated C-C bonds with tert -butyl hypochlorite and water.

Duyi ShenChaoyue SunYun HanZhen LuoTing RenQin ZhangWenting HuangJianru XieYing JiaMianran Chao
Published in: Organic & biomolecular chemistry (2024)
Herein we report 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 commercially available tert -butyl hypochlorite ( t BuOCl) was employed as a suitable chlorinating reagent, being accompanied by the less harmful t BuOH as the by-product. In addition, the oxygen atoms in the products came from water rather than molecular oxygen, based on the 18 O-labelling experiments. Meanwhile, the diastereoselectivity of the Z - and the corresponding E -alkenes has been compared and rationalized. Using a group of control experiments, the possible mechanisms have been proposed as the initial electrophilic chlorination of unsaturated C-C bonds in a Markovnikov-addition manner in general followed by a nucleophilic addition with water. This work simplified the oxychlorination method with a mild chlorine source and a green oxygen source under ambient conditions.
Keyphrases
  • drinking water
  • air pollution
  • randomized controlled trial
  • particulate matter