Biomimetic synthesis of equisetin and (+)-fusarisetin A.
Biomimetic synthesis of equisetin and (+)-fusarisetin A.
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DOI：
10.1002/chem.201302163
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发表时间：
2013-09
期刊：
影响因子：
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通讯作者：
Jun-Lin Yin;Lili Kong;Cheng Wang;Ying Shi;S. Cai;Shuanhu Gao
中科院分区：
文献类型：
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作者：
Jun-Lin Yin;Lili Kong;Cheng Wang;Ying Shi;S. Cai;Shuanhu Gao
（+）-Fusarisetin A属于一组具有潜在抗癌活性的酰基特特拉姆酸天然产物。木贼素是一种生物遗传学上相关的酰基特特拉姆酸，含有（+）-镰孢菌素A的基本骨架。我们提出木贼素和（+）-镰孢菌素A共享一条生物合成途径，该途径始于天然存在的（S）-丝氨酸和不饱和脂肪酸。为了支持这一假设，我们已经证明，环化序列涉及分子内的狄尔斯-阿尔德反应，然后由多烯基氨基酸的Dieckmann环化产生木贼素。在Mn（III）/O2或可见光化学产生的活性氧（ROS）的促进下，木贼素的有氧氧化产生过氧镰刀菌素，其可以容易地还原为（+）-镰刀菌素A。本文报道了木贼素和（+）-镰孢菌素A的生物合成的详细信息。
(+)-Fusarisetin A belongs to a group of acyl tetramic acid natural products that show potential anticancer activity. Equisetin, a biogenetically related acyl tetramic acid, contains the basic skeleton of (+)-fusarisetin A. We proposed that equisetin and (+)-fusarisetin A share a biosynthetic pathway that starts with naturally occurring (S)-serine and an unsaturated fatty acid. In support of this hypothesis, we have demonstrated that a cyclization sequence involving an intramolecular Diels-Alder reaction followed by a Dieckmann cyclization of polyenoylamino acid yielded equisetin. The aerobic oxidation of equisetin, promoted by either Mn(III)/O2 or a reactive oxygen species (ROS) produced by visible-light chemistry, gave peroxyfusarisetin, which could be easily reduced to (+)-fusarisetin A. We report herein detailed information on the biogenetic synthesis of equisetin and (+)-fusarisetin A.