Selective Conversion of 5-Hydroxymethylfuraldehyde Using Cp*Ir Catalysts in Aqueous Formate Buffer Solution.
Selective Conversion of 5-Hydroxymethylfuraldehyde Using Cp*Ir Catalysts in Aqueous Formate Buffer Solution.
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DOI：
10.1002/cssc.201501625
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发表时间：
2016-05
期刊：
影响因子：
8.4
通讯作者：
Wei-Peng Wu;Yong‐Jian Xu;R. Zhu;Min-shu Cui;Xing-Long Li;Jin Deng;Yao Fu
中科院分区：
文献类型：
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作者：
Wei-Peng Wu;Yong‐Jian Xu;R. Zhu;Min-shu Cui;Xing-Long Li;Jin Deng;Yao Fu
均相 Cp*Ir(III) 半夹心配合物催化 5-羟甲基糠醛 (5-HMF) 高选择性加氢/水解开环反应生成 1-羟基-2,5-己二酮 (HHD)。研究发现调节 pH 值可以调节产物的分布和反应选择性，并且在 pH 2.5 时实现了 5-HMF 完全转化为 HHD，选择性为 99%。机理研究表明，2,5-双-(羟甲基)呋喃的水解/开环反应是重要的中间反应步骤。此外，在10 g规模的实验中，HHD的分离收率达到85%，并且由于催化剂在酸性条件下具有优异的耐受性，以果糖为起始原料的反应也导致HHD的GC收率达到98%（果糖为71.9%）。
The highly selective hydrogenation/hydrolytic ring-opening reaction of 5-hydroxymethylfuraldehyde (5-HMF) was catalyzed by homogeneous Cp*Ir(III) half-sandwich complexes to produce 1-hydroxy-2,5-hexanedione (HHD). Adjustment of pH was found to regulate the distribution of products and reaction selectivity, and full conversion of 5-HMF to HHD with 99 % selectivity was achieved at pH 2.5. A mechanistic study revealed that the hydrolysis/ring-opening reaction of 2,5-bis-(hydroxymethyl)furan is the important intermediate reaction step. In addition, an isolated yield of 85 % for HHD was obtained in a 10 g-scale experiment, and the reaction with fructose as the starting material also led to a 98 % GC yield (71.9 % to fructose) of HHD owing to the excellent tolerance of the catalyst under acidic conditions.