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Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C\u2212H activation of in situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge\u2010driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in situ observed Pd\u2010hydride, Pd\u2010formyl and Pd\u2010acyl species.<\/jats:p>","DOI":"10.1002\/anie.202011152","type":"journal-article","created":{"date-parts":[[2020,11,5]],"date-time":"2020-11-05T03:18:50Z","timestamp":1604546330000},"page":"3422-3427","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Reaction Mechanism of Pd\u2010Catalyzed \u201cCO\u2010Free\u201d Carbonylation Reaction Uncovered by In Situ Spectroscopy: The Formyl Mechanism"],"prefix":"10.1002","volume":"60","author":[{"given":"Robert","family":"Geitner","sequence":"first","affiliation":[{"name":"Inorganic Chemistry and Catalysis Group Debye Institute for Nanomaterials Science Utrecht University  Universiteitsweg 99 3584 CG Utrecht The 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