Nature Chemistry ( IF 19.2 ) Pub Date : 2023-07-13 , DOI: 10.1038/s41557-023-01251-9 Dougal J Ritson 1 , John D Sutherland 1
Over the past few years, evidence has accrued that demonstrates that terrestrial photochemical reactions could have provided numerous (proto)biomolecules with implications for the origin of life. This chemistry simply relies on UV light, inorganic sulfur species and hydrogen cyanide. Recently, we reported that, under the same conditions, reduced phosphorus species, such as those delivered by meteorites, can be oxidized to orthophosphate, generating thiophosphate in the process. Here we describe an investigation of the properties of thiophosphate as well as additional possible means for its formation on primitive Earth. We show that several reported prebiotic reactions, including the photoreduction of thioamides, carbonyl groups and cyanohydrins, can be markedly improved, and that tetroses and pentoses can be accessed from hydrogen cyanide through a Kiliani–Fischer-type process without progressing to higher sugars. We also demonstrate that thiophosphate allows photochemical reductive aminations, and that thiophosphate chemistry allows a plausible prebiotic synthesis of the C5 moieties used in extant terpene and terpenoid biosynthesis, namely dimethylallyl alcohol and isopentenyl alcohol.
中文翻译:
硫代磷酸盐光化学使益生元能够获取糖和萜类前体
在过去的几年里,越来越多的证据表明,陆地上的光化学反应可能提供了大量对生命起源有影响的(原始)生物分子。这种化学反应仅依赖于紫外线、无机硫物质和氰化氢。最近,我们报道称,在相同条件下,还原磷物质(例如陨石释放的磷物质)可以被氧化为正磷酸盐,并在此过程中生成硫代磷酸盐。在这里,我们描述了对硫代磷酸盐性质的研究以及其在原始地球上形成的其他可能方法。我们表明,一些报道的益生元反应,包括硫代酰胺、羰基和氰醇的光还原,可以得到显着改善,并且可以通过 Kiliani-Fischer 型过程从氰化氢中获得丁糖和戊糖,而无需进展为高级糖。我们还证明硫代磷酸盐允许光化学还原胺化,并且硫代磷酸盐化学允许现有萜烯和类萜生物合成中使用的C 5部分(即二甲基烯丙醇和异戊烯醇)的合理的益生元合成。