A central feature of most lignocellulosic-biomass-valorization strategies is the depolymerization of all its three major constituents: cellulose and hemicellulose to simple sugars, and lignin to phenolic monomers. However, reactive intermediates, generally resulting from dehydration reactions, can participate in undesirable condensation pathways during biomass deconstruction, which have posed fundamental challenges to commercial biomass valorization. Thus, new strategies specifically aim to suppress condensations of reactive intermediates, either avoiding their formation by functionalizing the native structure or intermediates or selectively transforming these intermediates into stable derivatives. These strategies have provided unforeseen upgrading pathways, products and process solutions. In this Review, we outline the molecular driving forces that shape the deconstruction landscape and describe the strategies for chemical functionalization. We then offer an outlook on further developments and the potential of these strategies to sustainably produce renewable-platform chemicals.

大多数木质纤维素生物质增值策略的核心特征是其所有三种主要成分的解聚：纤维素和半纤维素解聚为单糖，木质素解聚为酚单体。然而，通常由脱水反应产生的反应性中间体可能会在生物质解构过程中参与不良的缩合途径，这对商业生物质增值提出了根本性挑战。因此，新的策略专门旨在抑制反应性中间体的缩合，通过将天然结构或中间体功能化来避免它们的形成，或者选择性地将这些中间体转化为稳定的衍生物。这些策略提供了不可预见的升级途径、产品和工艺解决方案。在这篇评论中，我们概述了塑造解构景观的分子驱动力，并描述了化学功能化的策略。然后，我们展望了进一步发展以及这些战略可持续生产可再生平台化学品的潜力。