Petroleum-derived aromatic compounds play irreplaceable roles in an extremely broad spectrum of industries. Production of value-added aromatic chemicals from renewable resources has been attractive and yet remains a great challenge for sustainable chemistry. We report herein a tandem catalytic oxidative aromatization approach that converts eucalyptus oil mixtures, renewable furans and dienes + dienophiles, to structurally diversified benzene derivatives. Eucalyptus oil mixtures undergo tandem dehydration–oxidative dehydrogenation to p-cymene. The Diels–Alder reaction between furans and dienophiles provides 7-oxanorbornene intermediates, which must be hydrogenated before dehydration–oxidative dehydrogenation to benzenoids in order to prevent retro-Diels–Alder side reactions. Cyclohexene intermediates resulted from DA reactions between nonfuran dienes and dienophiles undergo oxidative dehydrogenation to benzenoids. A heteropoly acid silicomolybdic acid acts as the catalyst, and molecular oxygen is the terminal oxidant for the key oxidative dehydrogenation reaction that is common for all the above reactions. These multistep sequences of reactions can be achieved in one pot without separation of intermediates.

中文翻译：

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通过串联催化将生物基化学物质氧化芳香化为苯衍生物

石油衍生的芳香族化合物在极为广泛的行业中扮演着不可替代的角色。由可再生资源生产增值芳烃化学品一直很有吸引力，但对于可持续化学而言仍然是巨大的挑战。我们在此报告了一种串联催化氧化芳构化方法，该方法将桉树油混合物，可再生呋喃和二烯+二烯亲和剂转化为结构上多样化的苯衍生物。桉树油混合物经过串联脱水-氧化脱氢生成p-cymene。呋喃与亲二烯体之间的狄尔斯-阿尔德反应提供了7-氧杂降冰片烯中间体，在脱水-氧化脱氢为苯类化合物之前必须进行氢化，以防止狄尔斯-阿尔德逆反应。非呋喃二烯与亲二烯体之间的DA反应产生的环己烯中间体经历氧化脱氢反应生成苯并类化合物。杂多酸硅钼酸充当催化剂，并且分子氧是所有上述反应所共有的关键氧化性脱氢反应的末端氧化剂。这些多步反应序列可以在一个罐中完成，而无需分离中间体。