7-Oxabicyclo[4.1.0]hept-3-ene, 1,6-dimethyl- (57338-10-0) 's Synthetic route

A Halide-Free Method for Olefin Epoxidation with 30% Hydrogen Peroxide

Sato, Kazuhiko  Aoki, Masao  Ogawa, Masami  Hashimoto, Tadashi  Panyella, David  Noyori, Ryoji

A catalytic system consisting of sodium tungstate dihydrate, (aminomethyl) phosphonic acid, and methyltrioctylammonium Hydrogensulfate, effects the epoxidation of olefins using 30% hydrogen peroxide with a substrate-to-catalyst molar ratio of 50 - 500. The reaction proceeds in high yield without solvents, or, alternatively, with added toluene under entirely halide-free conditions. Lipophilic ammonium hydrogensulfate, which replaces the conventional chloride, and an (α-aminoalkyl)phosphonic acid are crucial for the high reactivity. This method is operationally simple, environmentally benign, and much more economical than the oxidation with m-chloroperbenzoic acid, allowing for a large-scale preparation of epoxides. Various substrates including terminal olefins, 1,1- and 1,2-disubstituted olefins, cyclic olefins, and tri- and tetrasubstituted olefins as well as allylic alcohols, esters, α,β-unsaturated ketones, and ethers can be epoxidized in high yield. The scope and limitations of this new reaction system are discussed.