Aldehyde-Stabilization Strategies for Building Biobased Consumer Products around Intact lignocellulosic Structures.

Dwindling fossil resources and their associated environmental concerns have increased interest in biobased products. In particular, many approaches to convert lignocellulosic biomass into small-molecule building blocks are being explored via thermal, chemical, and biological processes. Depending on their structure, these molecules can be used as direct (i.e., drop-in) or indirect (different molecule from what is used today) substitutes for petrochemicals. In all such cases, biomass must be deconstructed, which involves the depolymerization of lignin and polysaccharides as well as their further transformation to produce these substitutes. Deconstruction often requires harsh conditions that cause degradation, and further upgrading implies multiple conversion steps, especially for drop-in molecules, all of which lead to low atom economy. Our group has developed an aldehyde-stabilization strategy that facilitates the depolymerization of lignocellulose to monomers in high yields by stabilizing intermediates under biomass deconstruction conditions. This strategy has now been adapted to prepare indirect substitutes for petrochemicals with very high atom economy including biobased solvents, plastic precursors, adhesives, and surfactants, which have widespread applications in modern society.In this Account, we first introduce the function of aldehydes using formaldehyde (FA) as an example. Specifically, we discuss their role in assisting lignin isolation and their ability to stabilize lignin by looking at the lignin monomer yields that can be obtained after hydrogenolysis of the associated aldehyde-functionalized lignin. Highly selective production of lignin monomers was achieved using acetaldehyde (AA) or propionaldehyde (PPA) as a stabilization reagent via either reductive or oxidative depolymerization. In a typical FA-assisted fractionation, hemicellulose was directly converted into diformylxylose (DFX), while cellulose with properties similar to those obtained by organosolv was isolated but could be converted to diformyl-glucose isomers (DFGs) by further hydrolysis. These stable molecules provide us a new method to preserve sugar molecules that often degrade during acidic fractionation, which will be discussed in Section 3. Besides, DFX can also be used as a green solvent (Section 4), while FA-lignin exhibits excellent adhesion properties for plywood preparation (Section 5). Biobased glyoxylic acid (GA) was used to convert hemicellulose into a high yield of dimethylglyoxylic-acid-xylose (DMGX), a terephthalic acid (TA) substitute for bioplastics production (Section 6), while GA-lignin demonstrates great amphiphilic properties and finds applications as surfactants in cosmetic products (Section 7). When fatty aldehydes were used as stabilization reagents, both lignin and hemicellulose were converted to surfactants by downstream defunctionalization (Section 7). We will also discuss the current limitations of this aldehyde-stabilization strategy for biomass utilization as well as potential solutions and improvements to said limitations. With this Account, we hope to spur further interest in aldehyde stabilization as a tool to deconstruct biomass and build new consumer products around functionalized and thus largely preserved natural structures.