通过1,4-迈克尔在Penicillium crustosum中形成烯和烯酸 添加来自Hydroxyclavatol的ortho-Quinone Methide到来自Crustosic Acid的γ-Butyrolactones
在PubMed上查看摘要
概括
此摘要是机器生成的。皮通过不同的基因集群产生A和B型皮. 关键酶如非还原性多基合成酶 ClaF 和细胞染色体P450 ClaJ 对于分别合成克拉瓦托和γ-丁烯酸至关重要.
科学领域
- 自然产品生物合成
- 菌群学
- 酵素学
背景情况
- 青素A和B是复杂的分子,其中包括γ-丁素和clavatol单位.
- 了解它们的生物合成是新化合物发现的关键.
研究的目的
- 为了阐明Penicillium crustosum中青素A和B生物合成的遗传和生化途径.
- 确定生产关键中间体的特定酶和反应.
主要方法
- 在Penicillium crustosum中进行基因集群识别和删除实验.
- 用前体分子进行养研究.
- 生物化学测试以表征酶活动.
主要成果
- 确定了两个负责关键构建块的不同基因集群.
- 非还原聚酸合成酶 ClaF 产生克拉瓦托.
- PKS-NRPS杂交的 TraA 合成皮质酸,从而产生陆地酸.
- 细胞染色体P450 ClaJ可以将酸转化为γ-丁.
- 克拉迪氧化了克拉瓦托,开始了非酶的迈克尔添加物,形成了阴茎动素.
结论
- 已经提出了涉及酶和非酶步骤的A和B素的详细生物合成途径.
- 在这些复杂的真菌代谢物组合中,特定的酶如 ClaF,TraA,ClaJ 和 ClaD 起着至关重要的作用.
相关概念视频
The attack of a nucleophile at the β carbon of an α,β-unsaturated carbonyl compound is called conjugate addition. Conjugate addition reactions of active methylene compounds, such as β-diketones, β-keto esters, β-keto nitriles, and α-nitro ketones, are called Michael addition reactions.
The reaction is catalyzed by a base that abstracts the acidic methylene hydrogen, generating a doubly-stabilized enolate ion that serves as the nucleophile or the Michael donor. The base employed depends...
α,β-Unsaturated carbonyl compounds with two electrophilic sites, the carbonyl carbon, and the β carbon, are susceptible to nucleophilic attack via two modes: conjugate or 1,4-addition and direct or 1,2-addition.
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are...
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
Conjugated dienes react with halogens in a similar manner. However, in addition to the 1,2-dihalide, they also form a 1,4-dihalide. The mechanism involves two steps.
First, a nucleophilic attack by one of the diene π bonds on the electrophilic center of the polarized halogen molecule forms a halonium ion intermediate. This is followed by a nucleophilic attack of the...
The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.
With conjugated systems like 1,3-butadiene, the addition of one equivalent of HBr yields a mixture of products: 1,2 and 1,4-addition products. As shown below, the mechanism involves the addition of H+ across one of the double bonds of the conjugated diene to form a resonance stabilized allyl cation. This is followed by the nucleophilic attack of...
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
The ring-forming reaction occurs in two stages: Michael addition and the subsequent intramolecular aldol condensation....

