The utilization of polymeric biorenewables for the synthesis of biofuels and essential chemicals is largely obstructed by their recalcitrant structures and complex product distribution. Here, hydrosilane-mediated hydrodeoxygenation (HDO) of the furanic mixture 5-hydroxymethylfurfural (HMF) and 5-chloromethylfurfural (CMF), directly derived from cellulosic biomass, can be enabled by heterogeneous Pd-catalyzed dechlorination to exclusively give the biofuel 2,5-dimethylfuran (DMF) in a high overall yield of 72%. Kinetic and isotope labeling studies supported by computational calculations explicitly elucidate the reaction pathways. The initial dechlorination of CMF into acidic species promotes the rapid in situ formation of relatively stable acetalized and etherified furanic intermediates, which not only greatly accelerate the reactivity of the entire HDO process (TOF: up to 1200 h⁻¹), but are also able to significantly get rid of unwanted side reactions. Importantly, this catalytic system can also be applied for the upgrade of various chlorinated carboxides to produce ortho-, meta- and para-substituted arenes with satisfactory yields of 82–99% at 25–45 °C, and the used commercial Pd/C catalyst is highly recyclable.

中文翻译：

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从纤维素原料液相合成呋喃生物燃料的反应的非均相（脱氯）控制

高分子生物可再生能源难以合成结构和复杂的产品分布大大阻碍了其用于合成生物燃料和基本化学品的利用。在此，通过异质钯催化脱氯可以直接衍生出纤维素生物质的呋喃混合物5-羟甲基糠醛（HMF）和5-氯甲基糠醛（CMF）的氢硅烷介导的加氢脱氧（HDO），可通过Pd催化的多氯联苯脱氯而仅得到生物燃料2,5 -二甲基呋喃（DMF），总产率高达72％。动力学和同位素标记研究得到了计算计算的支持，从而明确阐明了反应途径。CMF最初的脱氯成为酸性物质可促进原位快速降解形成相对稳定的乙缩醛和醚化呋喃中间体，不仅大大加快了整个HDO过程的反应性（TOF：高达1200 h ^-1），而且还能够显着消除不需要的副反应。重要的是，该催化系统还可用于各种氯化羧化物的提质，以生产邻，间和对位取代的芳烃，在25-45°C时具有82-99％的满意收率，以及使用的商用Pd / C催化剂是高度可回收的。