D-Excess-LaA Production Directly from Biomass by Trivalent Yttrium Species: Mechanism and Enantioselectivity
116 Pages Posted: 18 Jan 2019 Sneak Peek Status: PublishedMore...
D-Lactic acid (D-LaA) synthesis directly from actual biomass via chemocatalytic conversion has shown high potential for satisfying its enormous demand in widespread applications. Here we report yttrium (Y(III)) species catalyzed conversion of xylose and raw lignocelluloses to LaA with the highest yield of 87.3% (20% ee to D-LaA). Combining experiments with theoretical modelling, we reveal that [Y(OH)2(H2O)2]+ is the possible catalytically active species, enabling the unconventional cleavage of C3-C4 in xylulose and the subsequent dehydration of glyceraldehyde to pyruvaldehyde (PRA). The distinct interactions between hydrated-PRA and [Y(OH)2(H2O)2]+ species contribute to the formation of different enantiomers, wherein H-migration via re-face attack leads to L-LaA and that via si-face attack yields D-LaA. The lower strain energy barrier is the origin of excess D-enantiomer formation.
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