Arsenou Evaggelia S, Koutsourea Anna I, Fousteris Manolis A, Nikolaropoulos Sotiris S
Laboratory of Pharmaceutical Chemistry, School of Health Sciences, Department of Pharmacy, University of Patras, 26 500 Patras, Greece.
Steroids. 2003 May;68(5):407-14. doi: 10.1016/s0039-128x(03)00042-4.
A variety of delta5-steroids were converted into alpha, beta-unsaturated 7-ketones using a modification of the already known method of t-butyl hydroperoxide in the presence of copper iodide in acetonitrile. The same alteration was applied to another oxidative procedure, which had never been used before on steroidal substrates. The same oxidative agent was used in the presence of copper iodide, and tetra-n-butylammonium bromide was used as a phase-transfer catalyst in a two-phase system of water/methylene chloride. It was found that the allylic oxidation proceeded more efficiently when t-butyl hydroperoxide was added to the reaction mixture in portions. The initial addition of the total amount of oxidant or its dropwise addition afforded low yields. This observation contributes to the investigation of the reaction mechanism, and high-yield conversions of steroidal 5,6-enes into the corresponding conjugated 7-ones in short reaction times are reported.
使用在乙腈中碘化亚铜存在下叔丁基过氧化氢的已知方法的改进，将多种δ5-甾体转化为α，β-不饱和7-酮。同样的改变应用于另一种氧化程序，该程序以前从未用于甾体底物。在碘化亚铜存在下使用相同的氧化剂，并在水/二氯甲烷两相体系中使用四正丁基溴化铵作为相转移催化剂。发现当将叔丁基过氧化氢分批加入反应混合物中时，烯丙基氧化进行得更有效。初始加入总量的氧化剂或逐滴加入会导致产率较低。该观察结果有助于反应机理的研究，并报道了在短反应时间内甾体5,6-烯向相应共轭7-酮的高产率转化。
