硫代磷酸酯光化学可模拟生命起源前糖类和萜类化合物前体的构建

英国剑桥大学MRC分子生物学实验室John D. Sutherland研究团队利用硫代磷酸酯光化学，成功模拟了生命起源前糖类和萜类化合物前体的构建。2023年7月13日出版的《自然—化学》发表了这项成果。

在过去的几年中，已有很多累积证据表明，陆地光化学反应可以提供多种影响生命起源的（原型）生物分子。这种化学反应仅仅依靠紫外线、无机硫物种和氰化氢。最近，该课题组也报道，在相同的条件下，还原的含磷物种——例如由陨石带来的——可以被氧化为邻磷酸酯，并在这一过程中生成硫代磷酸酯。

在该研究中，科学家阐释了关于早期地球上硫代磷酸酯性质的研究，并描述了其在早期地球上多种可能形成的途径。研究者表明，一些报道过的生命起源前的反应，包括硫酰胺、羰基和氰醇的光致还原作用，可以被显著改进，而四糖和戊糖可以从氰化氢通过Kiliani-Fischer-type过程得到且不会进一步生成更高级别糖类。团队还展示了硫代磷酸酯允许光化学还原胺化作用，且硫代磷酸酯化学允许以一种合理的生命起源前化学合成C5砌块（即二甲基烯丙基醇和异戊醇），以用于多种萜烯和类萜的生物合成反应。

附：英文原文

Title: Thiophosphate photochemistry enables prebiotic access to sugars and terpenoid precursors

Author: Ritson, Dougal J., Sutherland, John D.

Issue&Volume: 2023-07-13

Abstract: 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.

DOI: 10.1038/s41557-023-01251-9

Source: https://www.nature.com/articles/s41557-023-01251-9

Nature Chemistry：《自然—化学》，创刊于2009年。隶属于施普林格·自然出版集团，最新IF：24.274 官方网址：https://www.nature.com/nchem/ 投稿链接：https://mts-nchem.nature.com/cgi-bin/main.plex