Glucose oxidation to formic acid and methyl formate in perfect selectivity

Abstract

<p>We report the highly remarkable discovery that glucose oxidation catalysed by polyoxometalates in methanolic solution enables formation of formic acid and methyl formate in close to 100% combined selectivity, thus with only negligible sugar oxidation to CO₂.</p>

Alcohol‐Activated Vanadium‐Containing Polyoxometalate Complexes in Homogeneous Glucose Oxidation Identified with 51V‐NMR and EPR Spectroscopy

“…In n‐propanol as well as in n‐butanol the same product compositions like using ethanol were detected. The combined yield of CO 2 and CO in both solvents are higher (45 % and 43 %) than in ethanol and nearly as high as in water [26] …”

“…We could unambiguously prove that the reaction mechanism in methanol differs from the common one in aqueous media. Especially the total oxidation to CO 2 can be completely supressed in methanol [26] . The impressive solvent effects were also recognized by Deng et.…”

“…In a previous study, some of our group investigated the effect of different solvents on the HPA‐5 catalysed reaction of glucose to formic acid [26] . Interestingly, significant differences in product selectivity were observed (see Table 1).…”

“…Based on mechanistic investigations using 13 C‐labelled glucose as a substrate, we could show that HPA‐5 catalysed glucose oxidation in methanolic solution leads to formic acid and further esterification to methyl formate as shown in Scheme 2 [26] …”

One-pot synthesis of formic acid via hydrolysis–oxidation of potato starch in the presence of cesium salts of heteropoly acid catalysts

“…2A). 4,46,47 The sufficient stability of formic acid in the hydrothermal medium at 423 K was conrmed by 11 hour experiments ( Fig. 2A).…”