AUTHOR=Yue Fengxia , Lan Wu , Zhang Liming , Lu Fachuang , Sun Runcang , Ralph John TITLE=Efficient Synthesis of Pinoresinol, an Important Lignin Dimeric Model Compound JOURNAL=Frontiers in Energy Research VOLUME=9 YEAR=2021 URL=https://www.frontiersin.org/journals/energy-research/articles/10.3389/fenrg.2021.640337 DOI=10.3389/fenrg.2021.640337 ISSN=2296-598X ABSTRACT=

Pinoresinol is a high-value monolignol-derived lignan used in plant defense and with human health-supporting effects. The synthetic yield and isolation efficiency of racemic pinoresinol from coniferyl alcohol by conventional radical coupling methods is sub-optimal. In this work, a facile and efficient synthetic approach was developed to synthesize pinoresinol with much higher yield. By using 5-bromoconiferyl alcohol, which was synthesized in high yield from 5-bromovanillin, to make 5,5′-bromopinoresinol via a peroxidase-mediated radical coupling reaction takes advantage of the smaller variety of radical coupling products from the 5-substituted monolignol, producing simpler product mixtures from which 5,5′-bromopinoresinol may be readily crystalized with good yield (total yield of 44.1% by NMR; isolated crystalline yield of 24.6%). Hydro-debromination of the crystalline 5,5′-bromopinoresinol to pinoresinol was essentially quantitative. Gram quantities of pinoresinol were conveniently synthesized by using this approach. This simple alternative pathway to make pinoresinol will impact pinoresinol-related research including structural characterization and modification of lignins, as well as clinical applications of pinoresinol and its derivatives.