Direct conversion of lignin to functionalized diaryl ethers via oxidative cross-coupling

Abstract

Abstract Efficient valorization of lignin, a sustainable source of functionalized aromatic products, would reduce dependence on fossil-derived feedstocks. Oxidative depolymerization is frequently applied to lignin to generate phenolic monomers. However, due to the instability of phenolic intermediates, repolymerization and dearylation reactions lead to low selectivity and product yields. Here, a highly efficient strategy to extract the aromatic monomers from lignin affording functionalized diaryl ethers using oxidative cross-coupling reactions is described, which overcomes the limitations of oxidative methods and affords high-value specialty chemicals. Reaction of phenylboronic acids with lignin converts the reactive phenolic intermediates into stable diaryl ether products in near-theoretical maximum yields (92% for beech lignin and 95% for poplar lignin based on the content of β−O−4 linkages). This strategy suppresses side reactions typically encountered in oxidative depolymerization reactions of lignin and provides a new approach for the direct transformation of lignin into valuable functionalized diaryl ethers, including key intermediates in pharmaceutical and natural product synthesis.