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A Simple and Effective Catalytic System for Epoxidation of Aliphatic Terminal Alkenes with Manganese(II) as the Catalyst
Author(s) -
Ho KamPiu,
Wong WingLeung,
Lam KinMing,
Lai CheukPiu,
Chan Tak Hang,
Wong KwokYin
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800759
Subject(s) - catalysis , manganese , chemistry , peracetic acid , selectivity , alkene , epoxide , organic chemistry , combinatorial chemistry , hydrogen peroxide
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 C 9 ‐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.