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13 pág.- 9 figuras.- 1 tabla.- 38 referencias.- The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fpls.2021.642848/full#supplementary-material, he monolignols, p-coumaryl, coniferyl, and sinapyl alcohol, arise from the general phenylpropanoid biosynthetic pathway. Increasingly, however, authentic lignin monomers derived from outside this process are being identified and found to be fully incorporated into the lignin polymer. Among them, hydroxystilbene glucosides, which are produced through a hybrid process that combines the phenylpropanoid and acetate/malonate pathways, have been experimentally detected in the bark lignin of Norway spruce (Picea abies). Several interunit linkages have been identified and proposed to occur through homo-coupling of the hydroxystilbene glucosides and their cross-coupling with coniferyl alcohol. In the current work, the thermodynamics of these coupling modes and subsequent rearomatization reactions have been evaluated by the application of density functional theory (DFT) calculations. The objective of this paper is to determine favorable coupling and cross-coupling modes to help explain the experimental observations and attempt to predict other favorable pathways that might be further elucidated via in vitro polymerization aided by synthetic models and detailed structural studies., JRa and HK were funded by the DOE Great Lakes Bioenergy Research Center (DOE Office of Science BER DE-SC0018409). JRe and JCR were funded by the Spanish Projects CTQ2014-60764-JIN and AGL2017-83036-R (financed by Agencia Estatal de Investigación, AEI and Fondo Europeo de Desarrollo Regional, FEDER).