Premium
Visible‐Light‐Mediated Synthesis of β‐Chloro Ketones from Aryl Cyclopropanes
Author(s) -
Petzold Daniel,
Singh Pardeep,
Almqvist Fredrik,
König Burkhard
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201902473
Subject(s) - aryl , chemistry , ketone , reagent , hydrochloric acid , catalysis , cyclopropane , functional group , combinatorial chemistry , nitric acid , photochemistry , organic chemistry , ring (chemistry) , alkyl , polymer
We report the visible‐light‐mediated synthesis of β‐chloro ketones from aryl cyclopropanes, oxygen, hydrochloric acid, and nitric acid. The operationally simple and catalyst‐free method uses cheap standard laboratory reagents and displays broad functional‐group tolerance. Moreover, scale up of the reaction and late‐stage functionalization of bioactive compounds is possible, providing the opportunity to utilize the cyclopropane ring as a masked β‐chloro ketone in a reaction sequence. We propose a light‐driven radical chain reaction initiated by the reaction of diluted hydrochloric and nitric acid to produce small quantities of molecular chlorine. The mechanistic hypothesis is supported by 18 O labelling and UV/Vis experiments, cyclovoltammetry, and several control reactions.