Intramolecular [2 + 2] Photocycloaddition of Altrenogest: Confirmation of Product Structure, Theoretical Mechanistic Insight, and Bioactivity Assessment
Intramolecular [2 + 2] Photocycloaddition of Altrenogest: Confirmation of Product Structure, Theoretical Mechanistic Insight, and Bioactivity Assessment
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Altrenogest 的分子内 [2 2] 光环加成：产物结构的确认、理论机制的洞察和生物活性评估
DOI：
10.1021/acs.joc.9b02070
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Wammer, Kristine H.
中科院分区：
文献类型：
--
作者：
Pflug, Nicholas C.;Patterson, Eric V.;Martinović-Weigelt, Dalma;Kolodziej, Edward P.;Gloer, James B.;McNeill, Kristopher;Cwiertny, David M.;Wammer, Kristine H.
在研究强效内分泌活性类固醇激素的环境命运时，我们观察到烯丙孕素（1）光解后形成了分子内[2 + 2]光环加成产物（2）和一个新的六环系统。通过X射线衍射分析确定了其结构和绝对构型。理论计算确定了一个无障碍的两步环化机制形成的2后光激发。2表现出孕激素，雌激素，雄激素和甾烷X受体活性，虽然一般与相对于1的效力降低。
While studying the environmental fate of potent endocrine-active steroid hormones, we observed the formation of an intramolecular [2 + 2] photocycloaddition product (2) with a novel hexacyclic ring system following the photolysis of altrenogest (1). The structure and absolute configuration were established by X-ray diffraction analysis. Theoretical computations identified a barrierless two-step cyclization mechanism for the formation of2upon photoexcitation.2exhibited progesterone, estrogen, androgen, and pregnane X receptor activity, albeit generally with reduced potency relative to1.