Menaquinone Biosynthesis: The Mechanism of 5,8-Dihydroxy-2-naphthoate Synthase (MqnD)
Menaquinone Biosynthesis: The Mechanism of 5,8-Dihydroxy-2-naphthoate Synthase (MqnD)
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甲萘醌生物合成：5,8-二羟基-2-萘甲酸酯合酶 (MqnD) 的机制
DOI：
10.1021/acs.biochem.1c00257
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发表时间：
2021
期刊：
影响因子：
2.9
通讯作者：
Begley, Tadhg P.
中科院分区：
文献类型：
--
作者：
Manion-Sommerhalter, Hannah R.;Fedoseyenko, Dmytro;Joshi, Sumedh;Begley, Tadhg P.
MqnD催化环去次黄嘌呤富塔苷(6)转化为5,8-二羟基-2-萘酸(7)和一种未表征的产物。本研究描述了一种化学酶法合成6。该合成通过使用柠檬酸钛（III）作为还原剂实现了2倍的收率提高，并使用脱氧黄嘌呤futalosine(5)的氟化类似物(5)通过ipso取代机制转化为6，实现了另外5倍的收率提高。该合成路线使6的合成量足够多，从而确定了第二个反应产物，并确定了mqnd催化的反应是通过半缩醛环开环-变异构化-反醛醇序列进行的。
MqnD catalyzes the conversion of cyclic dehypoxanthine futalosine (6) to 5,8-dihydroxy-2-naphthoic acid (7) and an uncharacterized product. This study describes a chemoenzymatic synthesis of6. This synthesis achieved a 2-fold yield enhancement by using titanium(III) citrate as the reducing agent and another 5-fold yield enhancement using a fluorinated analogue of dehypoxanthine futalosine (5) that was converted to6by an ipso substitution mechanism. This synthetic route enabled the synthesis of6in sufficient quantity to identify the second reaction product and to determine that the MqnD-catalyzed reaction proceeds by a hemiacetal ring opening–tautomerization–retroaldol sequence.