Biomimetic photocycloaddition of 3-hydroxyflavones: synthesis and evaluation of rocaglate derivatives as inhibitors of eukaryotic translation.
Biomimetic photocycloaddition of 3-hydroxyflavones: synthesis and evaluation of rocaglate derivatives as inhibitors of eukaryotic translation.
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DOI：
10.1002/anie.201003212
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发表时间：
2010-09-03
影响因子：
16.6
通讯作者：
Porco, John A., Jr.
中科院分区：
文献类型：
--
作者：
Roche, Stephane P.;Cencic, Regina;Pelletier, Jerry;Porco, John A., Jr.
米仔兰属植物产生许多次级代谢产物，包括环戊二烯并[B]苯并呋喃[1]罗格列酰胺1、司维司酚2和环戊二烯并[B，c]苯并吡喃[2]（糖苷类），包括波纳盆辛3（图1）。由于调节RNA解旋酶真核起始因子4A（eIF 4A）的活性，环戊[B]苯并呋喃天然产物具有强效抗癌特性，该因子参与翻译起始期间将核糖体装载到mRNA模板上，这是癌症中经常失调的一个步骤。[3]由于其不寻常的结构和重要的生物活性，罗格列胺1已成为许多研究小组的目标，并激发了许多优雅的合成策略。[4]我们已经报道了一种仿生的方法，环戊[B]苯并呋喃天然产物涉及的光环加成/酮醇移位重排/还原序列使用3-羟基黄酮（3-HF）衍生物，如4和肉桂酸甲酯5a。该策略使得能够利用3-HF的激发态分子内质子转移（ESIPT）全合成1和2（图1和方案1）[5]。4的光照射得到氧化吡喃鎓中间体6，其与肉桂酸甲酯5a进行[3+ 2]光环加成，得到相应的阿瓜兰核7a，其在两个步骤中转化为罗卡酸甲酯8a（方案1）。在本文中，我们描述了具有各种不同的光环加成的范围。
The plant genus Aglaia produces a number of secondary metabolites including the cyclopenta [b] benzofurans [1] rocaglamide 1, silvestrol 2, and cyclopenta [b, c] benzopyrans [2](aglains) including ponapensin 3 (Figure 1). Cyclopenta [b] benzofuran natural products possess potent anticancer properties due to modulation of the activity of the RNA helicase eukaryotic initiation factor 4A (eIF4A), which is involved in loading ribosomes onto mRNA templates during translation initiation, a step frequently deregulated in cancer.[3] Due to its unusual structure and important biological activity, rocaglamide 1 has been targeted by many research groups and has inspired a number of elegant synthetic strategies.[4] We have reported a biomimetic approach to cyclopenta [b] benzofuran natural products involving a photocycloaddition/ketol shift rearrangement/reduction sequence using 3-hydroxyflavone (3-HF) derivatives such as 4 and methyl cinnamate 5a. This strategy enabled total syntheses of both 1 and 2 (Figure 1 and Scheme 1)[5] utilizing excited state intramolecular proton transfer (ESIPT) of 3-HF’s. Photoirradiation of 4 affords the oxidopyrylium intermediate 6 which undergoes [3+ 2] photocycloaddition with methyl cinnamate 5a to provide the corresponding aglain core 7a, which was converted to methyl rocaglate 8a in two steps (Scheme 1). Herein, we describe the scope of the photocycloaddition with various
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影响因子：
15
作者：
Gerard, Baudouin;Sangji, Sheharbano;Porco, John A., Jr.
通讯作者：
Porco, John A., Jr.
影响因子：
3.6
作者：
BISCHOFBERGER, N;WALKER, KAM
通讯作者：
WALKER, KAM
影响因子：
1.7
作者：
Cabeza, M;Heuze, I;Martínez, R
通讯作者：
Martínez, R
DOI：
10.1039/c39720000494
发表时间：
1972-01-01
影响因子：
--
作者：
COCHRAN, TG;ABRAHAM, DJ;MARTIN, LL
通讯作者：
MARTIN, LL
影响因子：
--
作者：
BREWER, WE;STUDER, SL;CHOU, PT
通讯作者：
CHOU, PT