Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; Crowley, Michael F.

doi:10.1021/acs.jafc.6b02234

Title: Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

Journal Article · Sat May 28 00:00:00 EDT 2016 · Journal of Agricultural and Food Chemistry

DOI:https://doi.org/10.1021/acs.jafc.6b02234· OSTI ID:1259259

Elder, Thomas ^[1]; Berstis, Laura ^[2]; Beckham, Gregg T. ^[2]; Crowley, Michael F. ^[3]

USDA-Forest Service, Auburn, AL (United States). Southern Research Station
National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
National Renewable Energy Lab. (NREL), Golden, CO (United States). Biosciences Center

The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the $$\alpha$$-O cleavage reaction is lower than that of the $$\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1259259

Report Number(s):: NREL/JA-5100-66685

Journal Information:: Journal of Agricultural and Food Chemistry, Vol. 64, Issue 23; ISSN 0021-8561

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
5-hydroxyconiferyl alcohol
benzodioxane
coniferyl alcohol
lignin
stereochemistry

Title: Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

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