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/TiO₂, affording a high yield of 85.4% on a molar basis of glyoxylic acid at 110 °C and 1.0 MPa H₂. 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/TiO₂ and MoO_x/TiO₂ in a high yield of 86.2% at 200 °C and 2.0 MPa H₂. 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，用途广泛。然而，他们的合成过程仍然不是绿色和高效的。在此，我们报道了一种新颖的一锅法，用于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成 2-羟基-4-氧代戊二酸，然后在 Pd/TiO₂ 上连续脱水和氢化而合成的，在 110 °C 和 1.0 MPa H₂ 下，乙醛酸的摩尔基产量高达 85.4%。MTA 的合成涉及 KGA 和乙醛酸的交叉羟醛缩合成 3-（羧甲基）-2-羟基-4-氧代戊二酸，随后在 Pd/TiO₂ 和 MoO_x/TiO₂ 上加氢脱氧，在 200 °C 和 2.0 MPa H₂ 下以 86.2% 的高产率。这种新颖的方法为可持续生产各种仍然不容易获得的多功能羧酸提供了理论依据。