This study focuses on increasing the selectivity to methyl lactate from sugars using stannosilicates as heterogeneous catalyst. All group I ions are found to have a promoting effect on the resulting methyl lactate yield. Besides, the alkali ions can be added both during the preparation of the catalyst or directly to the solvent mixture to achieve the highest reported yield of methyl lactate (ca. 75 %) from sucrose at 170 °C in methanol. The beneficial effect of adding alkali to the reaction media applies not only to highly defect-free Sn-Beta prepared through the fluoride route, but also to materials prepared by post-treatment of dealuminated commercial Beta zeolites, as well as ordered mesoporous stannosilicates, in this case Sn-MCM-41 and Sn-SBA-15. These findings open the door to the possibility of using other preparation methods or different Sn-containing silicates with equally high methyl lactate yields as Sn-Beta.
The dehydration of glucose and other hexose carbohydrates to 5-(hydroxymethyl)furfural (HMF) was investigated in imidazolium-based ionic liquids with boric acid as a promoter. A yield of up to 42% from glucose and as much as 66% from sucrose was obtained. The yield of HMF decreased as the concentration of boric acid exceeded one equivalent, most likely as a consequence of stronger fructose-borate chelate complexes being formed. Computational modeling with DFT calculations confirmed that the formation of 1:1 glucose-borate complexes facilitated the conversion pathway from glucose to fructose. Deuterium-labeling studies elucidated that the isomerization proceeded via an ene-diol mechanism, which is different to that of the enzyme-catalyzed isomerization of glucose to fructose. The introduced non-metal system containing boric acid provides a new direction in the search for catalyst systems allowing efficient HMF formation from biorenewable sources.
Chemical processes capable of reducing the high oxygen content of biomass-derived polyols are in demand in order to produce renewable substitutes for chemicals of fossil origin. Deoxydehydration (DODH) is an attractive reaction that in a single step transforms a vicinal diol into an alkene, but the reaction requires a homogeneous catalyst, a reductant, and a solvent, which are typically expensive, unsustainable, or inefficient. Herein, we present the use of molybdenum(VI)-based compounds, in particular the cheap and commercially available (NH 4 ) 6 Mo 7 O 24 •4H 2 O, as catalysts for the DODH of vicinal diols in isopropyl alcohol ( i PrOH), which serves as both the solvent and reductant. The reaction proceeds at 240−250 °C in a pressurized autoclave, and the alkene yield from simple aliphatic diols can be as high as 77%. The major byproducts are carbonyl compoundsformed by dehydration of the dioland the alcohols formed by transfer hydrogenation of the carbonyl compounds; the total yield of reduced species (i.e., alkene and alcohols) can be as high as 92%. The DODH of glycerol yields allyl alcohol, which undergoes subsequent Mo-catalyzed deoxygenation to propylene driven by the oxidation of i PrOH; a major byproduct is the homocoupled product 1,5-hexadiene. Further insight in this Mo-catalyzed deoxygenation is gained by an investigation of model compounds: The allylic alcohol 1-hexen-3-ol is deoxygenated to hexene isomers in a yield of 65%, while benzyl alcohol is deoxygenated to toluene in a yield of 93%. The DODH of erythritol yields 39% 2,5-dihydrofuran, while the DODH of the proposed intermediate 1,4-anhydroerythritol yields 75%. The mechanism of the DODH of 1,4-anhydroerythritol was investigated by means of density functional theory (DFT), and the rate-determining step (24.1 kcal/mol) was found to be reduction of a molybdenum(VI) diolate to a molybdenum(IV) diolate.
Non-natural peptide analogs have significant potential for the development of new materials and pharmacologically active ligands. One such architecture, the β-peptoids (N-alkyl-β-alanines), has found use in a variety of biologically active compounds but has been sparsely studied with respect to folding propensity. Thus, we here report an investigation of the effect of structural variations on the cis−trans amide bond rotamer equilibria in a selection of monomer model systems. In addition to various side chain effects, which correlated well with previous studies of α-peptoids, we present the synthesis and investigation of cis−trans isomerism in the first examples of peptoids and β-peptoids containing thioamide bonds as well as trifluoroacetylated peptoids and β-peptoids. These systems revealed an increase in the preference for cis-amides as compared to their parent compounds and thus provide novel strategies for affecting the folding of peptoid constructs. By using NMR spectroscopy, X-ray crystallographic analysis, and density functional theory calculations, we present evidence for the presence of thioamide−aromatic interactions through C sp 2 −H•••S amide hydrogen bonding, which stabilize certain peptoid conformations.
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