Model studies of β-scission ring-opening reactions of cyclohexyloxy radicals:: Application to thermal rearrangements of dispiro-1 2,4-trioxanes
Model studies of β-scission ring-opening reactions of cyclohexyloxy radicals:: Application to thermal rearrangements of dispiro-1 2,4-trioxanes
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DOI：
10.1021/ol702534d
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发表时间：
2007-12-20
期刊：
影响因子：
5.2
通讯作者：
Taylor, Benjamin J.
中科院分区：
文献类型：
--
作者：
Erhardt, Stefan;Macgregor, Stuart A.;Taylor, Benjamin J.
对模型环己氧基(8a-c，9)的密度泛函研究表明，(A)邻氧原子的存在和(B)环上的α-取代基，特别是甲氧基，加速了β-开环反应的速度。与理论结果一致的是，甲氧基取代的二螺-1，2，4-三氧六环10的热分解得到了结构新颖的14元大环酮内酯11作为主要分离产物。
A DFT study of model cyclohexyloxy radicals (8a-c, 9) show that (a) the presence of an adjacent oxygen atom, and (b) alpha-substituents on the cyclohexyl ring, particularly methoxy, accelerate the rate of beta-scission ring-opening reactions. Consistent with theoretical results, thermolysis of the methoxy-substituted dispiro-1,2,4-trioxane 10 afforded the structurally novel, 14-membered macrocyclic keto lactone 11 as the major isolable product.