Tokuyasu Takahiro, Kunikawa Shigeki, McCullough Kevin J, Masuyama Araki, Nojima Masatomo
Department of Materials Chemistry & Frontier Research Center, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
J Org Chem. 2005 Jan 7;70(1):251-60. doi: 10.1021/jo048359j.
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.
在两种烯烃与Co(II)/O(2)/Et(3)SiH的混合物的竞争性过氧化反应中，发现烯烃底物的相对反应活性受三个主要因素影响：(1) 烯烃与HCo(III)络合物反应形成的中间体碳中心自由基的相对稳定性，(2) C=C双键周围的空间效应，以及(3) 与C=C双键相关的电子因素。与简单烯烃的结果一致，二烯烃的化学和区域选择性过氧化反应也得以实现。根据二烯烃的结构，产物不仅包括预期的无环不饱和三乙基硅基过氧化物，还包括通过不饱和过氧自由基中间体的分子内环化形成的1,2-二氧戊环和1,2-二氧六环衍生物。
