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Research Article Open access CC BY 4.0

Mo2C as Pre-Catalyst for the C-H Allylic Oxygenation of Alkenes and Terpenoids in the Presence of H2O2

Michael G. Kallitsakis, Dimitra K. Gioftsidou, Marina A. Tzani, Panagiotis A. Angaridis, Michael A. Terzidis, Ioannis N. Lykakis

Organics · pp. 173–186 · Published 4 Jul 2022

10.3390/org3030014

Abstract

In this study, commercially available molybdenum carbide (Mo2C) was used, in the presence of H2O2, as an efficient pre-catalyst for the selective C-H allylic oxygenation of several unsaturated molecules into the corresponding allylic alcohols. Under these basic conditions, an air-stable, molybdenum-based polyoxometalate cluster (Mo-POM) was formed in situ, leading to the generation of singlet oxygen (1O2), which is responsible for the oxygenation reactions. X-ray diffraction, SEM/EDX and HRMS analyses support the formation mainly of the Mo6O192− cluster. Following the proposed procedure, a series of cycloalkenes, styrenes, terpenoids and methyl oleate were successfully transformed into hydroperoxides. After subsequent reduction, the corresponding allylic alcohols were produced with good yields and in lab-scale quantities. A mechanistic study excluded a hydrogen atom transfer pathway and supported the twix-selective oxygenation of cycloalkenes on the more sterically hindered side via the 1O2 generation.

Allylic rearrangement Chemistry Catalysis Steric effects Polyoxometalate Photochemistry Molecule Terpenoid

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