烯丙基重排
化学
催化作用
位阻效应
多金属氧酸盐
光化学
萜类
分子
有机化学
药物化学
立体化学
作者
Michael G. Kallitsakis,Dimitra K. Gioftsidou,Marina A Tzani,Panagiotis A. Angaridis,Michael A. Terzidis,Ioannis N. Lykakis
出处
期刊:Organics
[MDPI AG]
日期:2022-07-04
卷期号:3 (3): 173-186
摘要
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.
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