Silicon-containing heterocyclic compounds cis- and trans-4a,8a-dimethyl-4a,8a-disiladecalin. Synthesis and oxidation with peroxides
作者:Kohei Tamao、Makoto Kumada
DOI:10.1016/s0022-328x(00)87460-4
日期:1971.8
the cis and trans isomers of(I) underwent oxidation very easily when treated with perbenzoic acid, giving the cis isomer of 1,6-dimethyl-11-oxa-1,6-disilabicyclo [4.4.1] undecane (IV). No trans-(IV) was formed at all. Oxidations with bis(trimethylsily) peroxide and oxygen afforded similar results. A mechanism for the formation of cis-(IV) from trans-(I) in the perbenzoic acid oxidation is proposed.
所述的反应顺-1,2-二氟-1,2-二甲基-1,2-二硅的异构体(IIIb)的与BrMg(CH 2)4 MgBr,得到顺式4a的异构体,8α二甲基4A,8A-双硅萘啶(I)为唯一产品。另一方面,与(IIIb)的反式异构体的反应产生比例为1 / 0.6的顺式和(I)的反式异构体的混合物。(I)的结构分配主要基于NMR光谱。用过苯甲酸处理时,(I)的顺式和反式异构体都非常容易氧化,从而形成顺式1,6-二甲基-11-oxa-1,6-二硅双环[4.4.1]十一烷(IV)的异构体。无反式-成立于所有(IV)。用双(三甲基甲硅烷基)过氧化物和氧气氧化可得到相似的结果。提出了在过苯甲酸氧化反应中由反式-(I)形成顺式-(IV)的机理。