A simple and effective catalytic system for epoxidation of aliphatic terminal alkenes with manganese(II) as the catalyst.
A simple catalytic system that uses commercially available manganese(II) perchlorate as the catalyst and peracetic acid as the oxidant is found to be very effective in the epoxidation of aliphatic terminal alkenes with high product selectivity at ambient temperature. Many terminal alkenes are epoxidised efficiently on a gram scale in less than an hour to give excellent yields of isolated product (>90 %) of epoxides in high purity. Kinetic studies with some C9-alkenes show that the catalytic system is more efficient in epoxidising terminal alkenes than internal alkenes, which is contrary to most commonly known epoxidation systems. The reaction rate for epoxidation decreases in the order: 1-nonene>cis-3-nonene>trans-3-nonene. ESI-MS and EPR spectroscopic studies suggest that the active form of the catalyst is a high-valent oligonuclear manganese species, which probably functions as the oxygen atom-transfer agent in the epoxidation reaction.
Ho
Kam-Piu
KP
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom Kowloon, Hong Kong SAR.
Wong
Wing-Leung
WL
Lam
Kin-Ming
KM
Lai
Cheuk-Piu
CP
Chan
Tak Hang
TH
Wong
Kwok-Yin
KY
D000097:Acetonitriles / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D004578:Electron Spin Resonance Spectroscopy; D004852:Epoxy Compounds / Q000737:chemistry*; D007700:Kinetics; D008345:Manganese / Q000737:chemistry*; D008670:Metals / Q000737:chemistry; D015394:Molecular Structure; D016877:Oxidants / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D014867:Water / Q000737:chemistry
D000097:Acetonitriles; D000475:Alkenes; D004852:Epoxy Compounds; D008670:Metals; D016877:Oxidants; D014867:Water; D008345:Manganese; C032159:acetonitrile