Prebiotic Absolute Asymmetric Synthesis of d-Ribose on Wollastonite

IF 2.4 4区 化学 Q2 CHEMISTRY, ANALYTICAL
Chirality Pub Date : 2026-08-20 DOI:10.1002/chir.70139
Wendi Zhang, Yang Gao, Jiao Wang, Quanzheng Deng, Lu Han, Wanning Zhang, Yuxi Fang
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引用次数: 0

Abstract

ATP is the core substance of energy metabolism in all forms of life. The chirality of d-ribose is essential for ATP's function, ensuring efficient molecular recognition, metabolic stability, and co-evolution with RNA in biological processes. However, origin of chirality of d-ribose is still unknown. Here, we demonstrate that wollastonite, an abundant Earth mineral, catalyzes the formose reaction between formaldehyde and glycolaldehyde and achieves high enantioselectivity (63.3%–91.3% ee) toward d-ribose. The lower energy barrier for the transition state of d-glyceraldehyde compared to that of l-glyceraldehyde, which possesses a similar configuration to glyceraldehyde, results in the enantioselective synthesis of ribose. Experimental and computational studies reveal that the surface chirality of wollastonite, which is characterized by its wavy atomic arrangement, selectively reduces the adsorption energy of the d-glyceraldehyde intermediate compared to its l-enantiomer. This preferential adsorption kinetically promotes the d-glyceraldehyde pathway and steers the reaction toward d-ribose. Our work establishes wollastonite as an intrinsically enantioselective mineral catalyst, provides a mechanistic foundation for prebiotic chiral selection toward d-ribose, and highlights surface design principles for asymmetric synthesis.

硅灰石上d-核糖的绝对不对称合成
ATP是所有生命形式能量代谢的核心物质。d-核糖的手性对ATP的功能至关重要,确保了有效的分子识别、代谢稳定性,并在生物过程中与RNA共同进化。然而,d-核糖手性的来源仍是未知的。在这里,我们证明了硅灰石,一种丰富的地球矿物,催化甲醛和乙醇醛之间的福尔摩反应,并对d-核糖具有高的对映选择性(63.3%-91.3% ee)。与具有类似构型的l-甘油醛相比,d-甘油醛的过渡态能垒较低,导致核糖的对映选择性合成。实验和计算研究表明,硅灰石的表面手性,以其波浪状的原子排列为特征,与l-对映体相比,选择性地降低了d-甘油醛中间体的吸附能。这种优先吸附在动力学上促进了d-甘油醛途径并将反应导向d-核糖。我们的工作确立了硅灰石作为一种内在的对映选择性矿物催化剂,为益生元对d-核糖的手性选择提供了机制基础,并强调了不对称合成的表面设计原则。
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来源期刊
Chirality
Chirality 医学-分析化学
CiteScore
4.40
自引率
5.00%
发文量
124
审稿时长
1 months
期刊介绍: The main aim of the journal is to publish original contributions of scientific work on the role of chirality in chemistry and biochemistry in respect to biological, chemical, materials, pharmacological, spectroscopic and physical properties. Papers on the chemistry (physiochemical, preparative synthetic, and analytical), physics, pharmacology, clinical pharmacology, toxicology, and other biological aspects of chiral molecules will be published.
文献相关原料
原料信息
原料厂家
1
Milli-Q synthesis system
2
calcium hydroxide
3
Calcium oxide
4
pyridine
5
d-glyceraldehyde
6
glycolaldehyde dimer
7
L-glyceraldehyde
8
Paraformaldehyde
9
trifluoroacetic anhydride
10
Chloroform
11
ethyl acetate
12
d-ribose
13
l-ribose
14
methylboronic acid
15
Silicon dioxide
16
22
Wollastonite
13983-17-0
¥64.00-¥5500.00
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