Conversion of substrate analogs suggests a Michael cyclization in iridoid biosynthesis.
Conversion of substrate analogs suggests a Michael cyclization in iridoid biosynthesis.
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DOI：
10.1016/j.chembiol.2014.09.010
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发表时间：
2014-11-20
影响因子：
--
通讯作者：
O'Connor SE
中科院分区：
文献类型：
--
作者：
Lindner S;Geu-Flores F;Bräse S;Sherden NH;O'Connor SE
环烯醚萜类单萜的核心结构是通过独特的环化反应形成的。催化该反应的酶环烯醚萜合酶在机理上不同于其他萜烯环化酶。在这里，我们描述了两个底物类似物的合成，以探讨环烯醚萜合酶的机制。这些底物类似物的酶促测定沿着来自天然底物的产物谱的线索强烈表明环烯醚萜合酶利用Michael反应来实现环化。这种改进的机制的理解将有利于开发的潜力环烯醚萜合成酶合成新的环状化合物从非天然底物。环烯醚萜合酶可以转化底物类似物环烯醚萜合酶产生其天然产物的开放和封闭形式。综合证据表明环烯醚萜合酶使用迈克尔反应。两种底物类似物的酶促测定，沿着来自天然底物的产物谱的线索，强烈表明环烯醚萜合酶利用迈克尔反应来实现环化。
The core structure of the iridoid monoterpenes is formed by a unique cyclization reaction. The enzyme that catalyzes this reaction, iridoid synthase, is mechanistically distinct from other terpene cyclases. Here we describe the synthesis of two substrate analogs to probe the mechanism of iridoid synthase. Enzymatic assay of these substrate analogs along with clues from the product profile of the native substrate strongly suggest that iridoid synthase utilizes a Michael reaction to achieve cyclization. This improved mechanistic understanding will facilitate the exploitation of the potential of iridoid synthase to synthesize new cyclic compounds from nonnatural substrates. Iridoid synthase can turn over substrate analogs Iridoid synthase yields both open and closed forms of its native product The combined evidence suggests that iridoid synthase uses a Michael reaction Enzymatic assay of two substrate analogs, along with clues from the product profile of the native substrate, strongly suggest that the iridoid synthase enzyme utilizes a Michael reaction to achieve cyclization.
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