124081-35-2Relevant articles and documents
Synthesis of cyclic peroxides by chemo- and regioselective peroxidation of dienes with Co(II)/O2/Et3SiH
Tokuyasu, Takahiro,Kunikawa, Shigeki,McCullough, Kevin J.,Masuyama, Araki,Nojima, Masatomo
, p. 251 - 260 (2007/10/03)
(Chemical Equation Presented). In the competitive peroxidation of mixtures of two alkenes with Co(II)/O2/Et3SiH, 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.
Co(III)-alkyl complex- and Co(III)-alkylperoxo complex-catalyzed triethylsilylperoxidation of alkenes with molecular oxygen and triethylsilane
Tokuyasu, Takahiro,Kunikawa, Shigeki,Masuyama, Araki,Nojima, Masatomo
, p. 3595 - 3598 (2007/10/03)
ROOCo(III) + Et3SiH → ROOSiEt3 + [HCo(III)] cat. ROOCo(III) or cat. RCo(III) R'CH=CH2 → R'CH(OOSiEt3)CH3 Et3SiH, O2 Both a Co(III)-alkyl complex and a Co(III)-alkylperoxo complex were found to catalyze triethylsilylperoxidation of alkenes with O2 and Et3SiH. On this basis, together with the nonstereoselectivity in the Co(II)-catalyzed peroxidation of 3-phenylindene and the formation of the corresponding 1,2-dioxolane from 2-phenyl-1-vinylcyclopropane (a radical clock), we propose a reasonable mechanism for the Co(II)-catalyzed novel autoxidation of alkenes with Et3SiH discovered by Isayama and Mukaiyama.
