Synthesis of cyclic peroxides by chemo- and regioselective peroxidation of dienes with Co(II)/O2/Et3SiH.
In the competitive peroxidation of mixtures of two alkenes with Co(II)/O(2)/Et(3)SiH, it was found that the relative reactivities of the alkene substrates are influenced by three major factors:. (1) relative stability of the intermediate carbon-centered radical formed by the reaction of the alkene with HCo(III) complex, (2) steric effects around the C=C double bond, and (3) electronic factors associated with the C=C double bond. Consistent with results from simple alkenes, the chemo- and regioselective peroxidation of dienes was also realized. Depending on the diene structure, the product included not only the expected acyclic unsaturated triethylsilyl peroxides but also 1,2-dioxolane and 1,2-dioxane derivatives via intramolecular cyclization of the unsaturated peroxy radical intermediates.
Tokuyasu
Takahiro
T
Department of Materials Chemistry & Frontier Research Center, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Kunikawa
Shigeki
S
McCullough
Kevin J
KJ
Masuyama
Araki
A
Nojima
Masatomo
M
D000466:Alkadienes / Q000737:chemistry*; D000962:Antimalarials / Q000138:chemical synthesis*; D037621:Artemisinins / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D008968:Molecular Conformation; D015394:Molecular Structure; D010545:Peroxides / Q000138:chemical synthesis*; D012717:Sesquiterpenes / Q000737:chemistry*
D000466:Alkadienes; D000962:Antimalarials; D037621:Artemisinins; D010545:Peroxides; D012717:Sesquiterpenes; C467230:yingzhaosu A; C031327:artemisinin