Structural Diversity of Perylenequinones Is Driven by Their Redox Behavior.
Structural Diversity of Perylenequinones Is Driven by Their Redox Behavior.
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DOI：
10.1021/acs.joc.1c02639
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发表时间：
2022-03-04
期刊：
影响因子：
--
通讯作者：
Hematian S
中科院分区：
文献类型：
--
作者：
Al Subeh ZY;Waldbusser AL;Raja HA;Pearce CJ;Ho KL;Hall MJ;Probert MR;Oberlies NH;Hematian S
竹红菌素和Hypomycins是真菌中的两个亚类，具有独特的结构、生物学和光化学性质。随着人们对这些天然光敏剂的兴趣越来越大，有必要进行更多的研究，以更好地了解这两个子类之间的结构关系。在这项研究中，长期假定的生物合成前体（7）的B类真菌的苝醌分离和表征从一个Shiraia样的sp.（菌株MSX 60519）。此外，还研究了竹红菌素和Hypomycins在好氧和厌氧条件下的电化学和化学氧化还原行为。这些研究用于定义竹红菌素内的结构关系（1-3），这进一步得到X射线晶体学的支持，以及竹红菌素和羟霉素之间的结构关系（4-6）。在厌氧条件下竹红菌素的化学还原确定了hypomycin A（4），hypomycin C（5）和hypomycin E（6）的来源，这反过来又证实了4并修改了5和6的绝对构型。竹红菌素被证明在有氧条件下进行可逆的还原和再氧化，而在厌氧环境和更长的时间尺度，完全还原的形式可以在一定程度上进行分子内闭环复分解。这可能赋予一种手段的还原途径对这些光毒素的自我保护，并解释在真菌代谢产物中观察到的化学多样性。
Hypocrellins and hypomycins are two subclasses of fungal perylenequinones with unique structural, biological, and photochemical properties. With the growing interest in these naturally occurring photosensitizers, more studies were warranted to better understand the structural relationships between these two subclasses of perylenequinones. In this study, the long-postulated biosynthetic precursor (7) of class B fungal perylenequinones was isolated and characterized from a Shiraia-like sp. (strain MSX60519). Furthermore, the electrochemical and chemical redox behaviors of hypocrellins and hypomycins were investigated under aerobic and anaerobic conditions. These studies served to define the structural relationship within hypocrellins (1–3), which was further supported by X-ray crystallography, and between hypocrellins and hypomycins (4–6). Chemical reductions of hypocrellins under anaerobic conditions identified the origin of hypomycin A (4), hypomycin C (5), and hypomycin E (6), which in turn served to confirm 4 and revise the absolute configurations of 5 and 6. Hypocrellins were shown to undergo reversible reduction and reoxidation under aerobic conditions, while in an anaerobic environment and longer time scale, the fully reduced form can, to some extent, undergo an intramolecular ring closing metathesis. This may impart a means of reductive pathway for self-protection against these phototoxins and explain the chemical diversity observed in the fungal metabolites.
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DOI：
10.1073/pnas.89.20.9588
发表时间：
1992-10-15
影响因子：
11.1
作者：
DAUB, ME;LEISMAN, GB;BOWDEN, EF
通讯作者：
BOWDEN, EF
影响因子：
5.1
作者：
Chooi, Yit-Heng;Zhang, Guozhi;Solomon, Peter S.
通讯作者：
Solomon, Peter S.
影响因子：
2.1
作者：
Krueger, Martin C.;Bergmann, Michael;Schlosser, Dietmar
通讯作者：
Schlosser, Dietmar
影响因子：
3.3
作者：
LEISMAN, GB;DAUB, ME
通讯作者：
DAUB, ME
影响因子：
2.6
作者：
Jiang, Yuan;Leung, Albert Wingnang;Xu, Chuanshan
通讯作者：
Xu, Chuanshan