Studies on The Application of The Paterno‐Buchi Reaction to The Synthesis of Novel Fluorinated Scaffolds
Studies on The Application of The Paterno‐Buchi Reaction to The Synthesis of Novel Fluorinated Scaffolds
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Paterno-Buchi反应在新型含氟支架合成中的应用研究
DOI：
10.1002/chem.202102621
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Hoffmann Norbert
中科院分区：
文献类型：
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作者：
Gomez Fernandez Mario Andres;Lefebvre Corentin;Sudau Alexander;Genix Pierre;Vors Jean‐Pierre;Abe Manabu;Hoffmann Norbert
在通过光化学反应获得新支架的背景下，描述了杂芳族、三氟甲基苯基酮和富电子烯烃之间产生氧杂环丁烷的Paternò-Büchi反应。随后对芳香酮与氟化烯烃的反应进行了全面的研究。根据氧杂环丁烷环上的取代模式，复分解反应被描述为产生单氟化烯烃的次要副反应过程。总的来说，最后一个反应对应于光维蒂希反应和电子等排体的产率。为了解释与这些烯烃发生的 Paternò-Büchi 反应的罕见区域选择性，我们测定了静电势衍生电荷 (ESP)。在第二项计算研究中，Paternò-Büchi 反应的典型 1,4-双自由基中间体的相对稳定性已被确定。结果很好地解释了区域选择性。氧杂环丁烷的进一步转化或氟代烯烃的先前官能化为氧杂环丁烷作为生物活性化合物的核心结构开辟了前景。
In the context of new scaffolds obtained by photochemical reactions, Paternò‐Büchi reactions between heteroaromatic, trifluoromethylphenyl ketone and electron rich alkenes to give oxetanes are described. A comprehensive study has then been carried out on the reaction of aromatic ketones with fluorinated alkenes. Depending on the substitution pattern at the oxetane ring, a metathesis reaction is described as a minor side process to give mono fluorinated alkenes. Overall, this last reaction corresponds to a photo‐Wittig reaction and yield amid isosteres. In order to explain the uncommon regioselectivity of the Paternò‐Büchi reaction with these alkenes, electrostatic‐potential derived charges (ESP) have been determined. In a second computational study, the relative stabilities of the typical 1,4‐diradical intermediates of the Paternò‐Büchi reaction have been determined. The results well explain the regioselectivity. Further transformations of the oxetanes or previous functionalization of the fluoroalkenes open perspectives for oxetanes as core structures for biologically active compounds.