The outcome of the oxidations of unusual enediamide motifs is governed by the stabilities of the intermediate iminium ions.

The outcome of the oxidations of unusual enediamide motifs is governed by the stabilities of the intermediate iminium ions.
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DOI:
10.1371/journal.pone.0047224
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发表时间:
2012
期刊:
影响因子:
3.7
通讯作者:
Todd MH
Todd MH
中科院分区:
综合性期刊3区
文献类型:
--
作者:
Ahamed M;Chan B;Jensen P;Todd MH

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我们比较了两个不寻常的“烯二酰胺”基序(3,4-二氢吡嗪-2(1H)-酮),其中一个双键两侧是两个酰胺的氧化的结果。在一种情况下,氧化导致开环产物所产生的双键的断裂,并在其他罕见的顺式双氧化合物得到。这两种产品的特征在于X射线晶体学。根据计算的中间体自由能,合理化的关键反应的结果。
We compare the results from the oxidation of two unusual “enediamide” motifs (3,4-dihydropyrazin-2(1H)-ones), where a double bond is flanked by two amides. In one case the oxidation led to a ring-opened product arising from the cleavage of the double bond, and in the other a rare cis-dioxygenated compound was obtained. Both products have been characterized by X-ray crystallography. The outcomes of the key reactions are rationalized based on calculated free energies of intermediates.
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