Ex Situ Generation of ¹⁸O₂ and ¹⁷O₂ from Endoperoxides for *O-Labeling and Mechanistic Studies of Oxidations by Dioxygen

Abstract

Near-stoichiometric amounts of 18O2 and 17O2 were generated ex situ from endoperoxides in a two-chamber glassware to oxidize various substrates. This strategy gave [*O2]­endoperoxides, [*O1]­quinones, [*O1]­phenols, and [*Ox]­artemisin in moderate to good yields and high isotopic enrichments (up to 84%) at affordable costs. Moreover, mass spectrometry and 17O NMR of the [*O]­products provided valuable information about the chemical mechanisms involved.

Two-Chamber-Enabled Hydrogenation Reactions Using Al-H2O/NaOH: Access to Pharmaceuticals

“…In 2011, Skrydstrup and co-workers developed the two-chamber reactor (COware) for the safe generation of gaseous reagents . In recent times, COware has been used for the ex situ generation of different gases, such as CO, H 2 , SO 2 , SO 2 F 2, HCN, O 2 etc., followed by various functional group transformations . Recently, we have reported aminocarbonylation reactions in COware using chloroform as a CO source .…”