Mechanistic studies on PET-oxidative cyclization of unsaturated silyl enol ethers:: dependence of the regioselectivity on alcohol addition and pressure effects
Mechanistic studies on PET-oxidative cyclization of unsaturated silyl enol ethers:: dependence of the regioselectivity on alcohol addition and pressure effects
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DOI：
10.1039/a807683i
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发表时间：
1999-04-01
期刊：
影响因子：
--
通讯作者：
Mattay, J
中科院分区：
文献类型：
--
作者：
Ackermann, L;Heidbreder, A;Mattay, J
不饱和甲硅烷基烯醇醚在电子转移敏化剂的存在下进行辐照。使用不同的敏化剂的环化反应的效率进行了研究。闭环反应的内消旋区域化学可以通过改变甲硅烷基或通过添加醇来控制。此外，区域化学对压力的依赖性被揭示，它似乎可以与乙腈作为亲核试剂在1500巴。作为关键中间体，涉及自由基阳离子和自由基。
Unsaturated silyl enol ethers are irradiated in the presence of electron transfer sensitizers. The efficiency of the cyclization reaction using different sensitizers is investigated. The endolexo regiochemistry of the ring closure reaction can either be controlled by variation of the silyl group or by addition of alcohol. Furthermore, a dependence of the regiochemistry on pressure is revealed and it seems that it can be related to acetonitrile acting as a nucleophile at 1500 bar. As key intermediates radical cations and radicals are involved.