Hong Cheng-Bin, Hua Wangde, Liu Lieke, Liu Haichao
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Nat Commun. 2025 Feb 1;16(1):1245. doi: 10.1038/s41467-025-56536-z.
α-Ketoglutaric acid (KGA) and methanetriacetic acid (MTA) are important multi-functional carboxylic acids with versatile applications. However, their synthetic processes are still not green and efficient. Herein, we report a novel one-pot approach for sustainable synthesis of KGA and MTA from biomass-derived pyruvic and glyoxylic acids under mild conditions. KGA is synthesized via cross-aldol condensation of pyruvic and glyoxylic acids to 2-hydroxy-4-oxopentanedioic acid, followed by its sequential dehydration and hydrogenation on Pd/TiO, affording a high yield of 85.4% on a molar basis of glyoxylic acid at 110 °C and 1.0 MPa H. The synthesis of MTA involves cross-aldol condensation of KGA and glyoxylic acid to 3-(carboxymethyl)-2-hydroxy-4-oxopentanedioic acid and its subsequent hydrodeoxygenation on Pd/TiO and MoO/TiO in a high yield of 86.2% at 200 °C and 2.0 MPa H. This novel approach provides a rationale for the sustainable production of various multi-functional carboxylic acids that are still not easily available.
α-酮戊二酸（KGA）和甲烷三乙酸（MTA）是重要的多功能羧酸，具有广泛的应用。然而，它们的合成过程仍然不够绿色和高效。在此，我们报道了一种新颖的一锅法，可在温和条件下从生物质衍生的丙酮酸和乙醛酸可持续合成KGA和MTA。KGA是通过丙酮酸和乙醛酸的交叉羟醛缩合反应生成2-羟基-4-氧代戊二酸，然后在Pd/TiO上依次进行脱水和氢化反应，在110°C和1.0MPa氢气条件下，以乙醛酸的摩尔计产率高达85.4%。MTA的合成涉及KGA和乙醛酸的交叉羟醛缩合反应生成3-(羧甲基)-2-羟基-4-氧代戊二酸，随后在200°C和2.0MPa氢气条件下在Pd/TiO和MoO/TiO上进行加氢脱氧反应，产率高达86.2%。这种新颖的方法为可持续生产各种仍不易获得的多功能羧酸提供了理论依据。
