Manganese-catalysed dehydrogenative oxidation of glycerol to lactic acid
Manganese-catalysed dehydrogenative oxidation of glycerol to lactic acid
复制标题
锰催化甘油脱氢氧化制乳酸
DOI：
10.1039/d2gc03235j
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发表时间：
2022
期刊：
影响因子：
9.8
通讯作者：
Yao Fu
中科院分区：
文献类型：
--
作者：
Chen-Qiang Deng;Jin Deng;Yao Fu
在这里，我们报道了一种由PNP配体支撑的明确的钳形锰络合物，用于甘油在二氢释放的情况下转化为乳酸钠。在温和的反应条件下，以Mn3络合物为催化剂，乳酸钠的收率为96%，选择性为96%。在该转化中，即使催化剂的负载量只有0.025%，也可以在36小时内获得高的反应活性和良好的选择性(最高可达98%)。机理研究表明，甘油脱氢主要由锰系催化剂负责，而氢氧化钠的用量对后续的Cannizzaro反应有重要影响。此外，还利用原位31P核磁共振波谱对反应中的催化活性物种进行了研究。该催化系统为将生物柴油废物转化为高价值化学品提供了一种绿色、高效和原子经济的方法。
Herein, we report a well-defined pincer manganese complex supported by PNP ligands for the conversion of glycerol to sodium lactate with dihydrogen liberation. Sodium lactate could be obtained in 96% yield with 96% selectivity under mild reaction conditions, with the Mn-3 complex as the catalyst. In this transformation, catalyst loadings even as low as 0.025 mol% could also result in high reactivity and excellent selectivity (up to 98%) at 180 °C in 36 hours. Mechanistic studies demonstrated that the manganese catalyst was mainly responsible for glycerol dehydrogenation, while the amount of sodium hydroxide had a crucial effect on the subsequent Cannizzaro reaction. In addition, the catalytically active species in the reaction were investigated by using in situ31P NMR spectroscopy. This catalytic system provides a green, efficient, and atom-economical approach for upgrading biodiesel waste into high-value chemicals.