Synthesis of a novel polyester building block from pentoses by tin-containing silicates

Abstract

C5-Sugars form a new bio-monomer (trans-2,5-dihydroxy-3-pentenoic acid methyl ester), which can undergo enzymatic copolymerization with E6-HH to form multifunctional polymers.

Quantitative NMR Approach to Optimize the Formation of Chemical Building Blocks from Abundant Carbohydrates

“…The use of NMR spectroscopy for component identification and quantification is particularly well-developed for biological samples,i ncluding biofluids, extracts,a nd foods, buth as also gainedp opularity within biomass conversion,f or instancei nt he study of carbohydrate isomerization reactions [15][16][17] or for lignin structure and depolymerization reactions. Band-selective 13 Ce xcitation [19] and optimized decoupling sequences [20,21] were used to suppress non-informative signals and artefacts and to obtain higher quality 1 H-13 C2 DN MR spectra.N MR spectroscopy has notoriouss hortcomings in the detection of heteroatoms, but this problemw as negligible for reactions involving carbohydrate fragmentation or dehydration,a so xygen positions could be inferredf rom 13 Cc hemical shifts. Specifically, DQF-COSY,T OCSY, 1 H-13 CH MBC, conventionala nd edited 1 H-13 CH SQC, as well as 1 H-13 CH SQC-TOCSY spectra were employedf or compound identification.…”

“…Biomass can be utilized to provide access to both existing and new types of buildingb locks, and research into this area has steeply increasedd uring the last decade. [12][13][14] Conversions of C5 and C6 carbohydratesi nto the acyclic unsaturated a-hydroxyc ompounds 1 and 12 have been achieved using Sn-Beta in methanol [13,14] or in water [12] at temperatures The future role of biomass-derivedc hemicals relies on the formation of diversefunctional monomers in high yields from carbohydrates. Directc onversion of sugars to at arget chemical by heterogeneous catalysis offers the best chance of lowering the process costs.…”

“…[12][13][14] C5 and C6 carbohydrates yield around3 0% for C5-carbohydrate substrate Me-1 and around1 5% for C6-carbohydrate substrate Me-12,r espectively. AS n-Betazeolite synthesized under hydrothermal conditions using hydrofluoric acid as the mineralizing agent was the most efficient catalystf or this reaction.…”

NMR Spectroscopic Isotope Tracking Reveals Cascade Steps in Carbohydrate Conversion by Tin‐Beta

“…[9] Subsequentr esearch has illuminateds ome mechanistic details of the reactions that form ML from triosesa nd hexoses in methanol solvent. [14][15][16][17][18][19][20] Most of these new products are a-hydroxy acids such as lactatea nd some show potentiala sp olymer buildingb locks. [14][15][16][17][18][19][20] Most of these new products are a-hydroxy acids such as lactatea nd some show potentiala sp olymer buildingb locks.…”

“…These developments resulted in increasingly feasible methods for tuning reactions electivity [1,4,[10][11][12][13][14] as well as the discovery of new reaction products. [18,[20][21][22][23] These bio-monomers include methyl 2,5,6-trihydroxy-3-hexenoate (THM),m ethyl 2,5-dihydroxy-3pentenoate (DPM),m ethyl vinyl glycolate (MVG), and assorted 3-deoxy esters (3DE) andl actones (3DL), the structures of which are shown in Figure1.P athways that lead to the formation of these compoundsh ave so far remained less comprehensively studied than those of lactatef ormation as these products were characterized more recently and because the key C 4 -C 6 intermediates are not as easily accessible in pure forms as the analogous C 3 compounds for use as reference standards and prospective reactions ubstrates. [18,[20][21][22][23] These bio-monomers include methyl 2,5,6-trihydroxy-3-hexenoate (THM),m ethyl 2,5-dihydroxy-3pentenoate (DPM),m ethyl vinyl glycolate (MVG), and assorted 3-deoxy esters (3DE) andl actones (3DL), the structures of which are shown in Figure1.P athways that lead to the formation of these compoundsh ave so far remained less comprehensively studied than those of lactatef ormation as these products were characterized more recently and because the key C 4 -C 6 intermediates are not as easily accessible in pure forms as the analogous C 3 compounds for use as reference standards and prospective reactions ubstrates.…”