C4 chemicals such as succinic acid and γ-butyrolactone are important industrial feedstocks. In this work, we present a flexible photoenzymatic route toward biobased C4 chemicals from furfural via fumaric semialdehyde (FSA). The high reactivity and plasticity of multifunctionalized FSA allow facile production of various C4 chemicals by slightly modifying multienzymatic cascades. Seven valuable C4 chemicals were obtained by sequential photoenzymatic and multienzymatic catalysis in 73%–92% yields. Synergistic catalysis by meso-tetra(4-carboxyphenyl)porphyrin (TCPP) and a basic resin enabled direct conversion of furfural into FSA. In photoenzymatic (E)-4-hydroxycrotonic acid synthesis involving TCPP, a space-time yield of up to 1.7 g L⁻¹ h⁻¹ and a total turnover number of 94,000 for an enzyme were achieved. Besides, gram-scale synthesis of four C4 chemicals was implemented in 60%–88% isolated yields. The photoenzymatic route centering FSA may work as an alternative route for the production of valuable C4 chemicals.

中文翻译：

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通过富马酸半醛从生物质衍生的糠醛光酶合成 C4 化学品


丁二酸、γ-丁内酯等C4化学品是重要的工业原料。在这项工作中，我们提出了一种灵活的光酶催化路线，从糠醛通过富马半醛（FSA）制备生物基 C4 化学品。多功能 FSA 的高反应性和可塑性允许通过稍微修改多酶级联来轻松生产各种 C4 化学品。通过连续光酶和多酶催化，获得了 7 种有价值的 C4 化学物质，产率为 73%–92%。内消旋四（4-羧基苯基）卟啉（TCPP）和碱性树脂的协同催化使糠醛直接转化为 FSA。在涉及 TCPP 的光酶 ( E )-4-羟基巴豆酸合成中，实现了高达 1.7 g L ^-1 h ^-1的时空产量和 94,000 的酶总周转数。此外，四种 C4 化学品的克级合成实现了 60%–88% 的分离产率。以 FSA 为中心的光酶路线可能作为生产有价值的 C4 化学品的替代路线。