Total synthesis of perylene quinone mycotoxins

霉菌侵染食物和饲料会导致农作物损失，真菌毒素(霉菌毒素)会严重影响健康。交链孢属的代谢物是一类较少被研究的毒素；特别重要的是间苯二酚内酯和二苯二酚。虽然一些二苯并二酚类毒素毒性很大，但几乎没有一种被彻底研究过，并不是所有的结构都不明确，也没有完全合成的方法，这可以为生物学研究提供足够数量的毒素。在这项建议中，我们描述了全合成，这将导致几种二苯并苯二酚毒素。具有联苯亚结构的毒素应可从萘-1，5-二醇或联苯-α，α‘-二醛获得，具有二氢菲亚结构的毒素可从四氢-1，5-二醇开始接近。关键反应包括烯化、亲电芳香族酰化和Meinwald重排。进一步的转化将是环氧化、环氧化物的开放、二羟基化以及羰基化合物的α、β-脱水，这取决于各自的目标毒素。

Infestation of food and feed with mould fungi leads to crop losses and due the fungal toxins (mycotoxins) to severe health problems. Alternaria metabolites are a less investigated class of toxins; especially important are the resorcylic lactones and the perylene quinones. Though some of the perylene quinone toxins are highly toxic, hardly any of these were thoroughly investigated, not all of their structures are not unambiguously clear, and no total synthesis is available, which could supply sufficient amounts of the toxins for biological investigations. In this proposal we describe total syntheses, which would lead to several perylene quinone toxins. Toxins with a biphenyl substructure should be accessible from either naphthalene-1,5-diol or from biphenyl-alpha,alpha'-dicarbaldehyde and toxins with a dihydroanthracene substructure could be approached starting with tetralin-1,5-diol. Key reactions would be inter alia olefinations, electrophilic aromatic acylations, and Meinwald rearrangements. Further transformation would be epoxidations, opening of epoxides, dihydroxylations, and alpha,beta-dehydrations of carbonyl compounds, depending on the respective target toxin.