Carbonylation reactions carried out at room temperature and at atmospheric pressure of carbon monoxide are highly attractive and extremely rare at the same time. Here, the oxidative alkoxycarbonylation of styrenes to industrially relevant cinnamates has been developed under such a mild conditions (rt, 1 atm of CO) in the presence of a palladium(II) complex bearing a bis(aryl)acenaphthenequinonediimine ligand, benzoquinone and -toluenesulfonic acid. Remarkably, variously substituted styrene derivatives have been efficiently carbonylated using a nearly stoichiometric amount of alcohols, with a dramatic reduction of waste. Even reluctant internal alkenes have shown to be compatible under these carbonylative conditions. In consideration of experimental results and DFT calculations a mechanistic rationale has been proposed. Based on this study, the benzoquinone has been found to promote the final palladium reoxidation, and to boost the reaction under such unprecedent mild conditions. The present methodology has been successfully exploited for the synthesis of high value-added cinnamoyl glycerols and cinnamic acid sugar esters, including the 6---coumaroyl-D-glucose natural product.

中文翻译：

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苯乙烯在室温下的多功能立体选择性氧化烷氧基羰基化

在室温和一氧化碳大气压下进行的羰基化反应非常有吸引力，同时也极其罕见。在这里，在带有双（芳基）苊醌二亚胺配体、苯醌和对甲苯磺酸的钯（II）络合物存在下，在如此温和的条件（室温，1 atm CO）下，将苯乙烯氧化烷氧基羰基化为工业相关的肉桂酸酯。酸。值得注意的是，各种取代的苯乙烯衍生物已经使用接近化学计量的醇进行了有效的羰基化，同时大大减少了废物。即使是不情愿的内烯烃也已显示出在这些羰基化条件下是相容的。考虑到实验结果和 DFT 计算，提出了机械原理。基于这项研究，发现苯醌可以促进钯的最终再氧化，并在前所未有的温和条件下促进反应。该方法已成功用于合成高附加值肉桂酰甘油和肉桂酸糖酯，包括6---香豆酰-D-葡萄糖天然产物。