Abstract

“CO‐free” carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received widespread attention in homogeneous catalysis lately. 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−H 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‐driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in situ observed Pd‐hydride, Pd‐formyl and Pd‐acyl species.

Highlights

  • Abstract: “CO-free” carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received widespread attention in homogeneous catalysis lately

  • “CO-free” carbonylation reactions have been successfully applied in organic synthesis[8] relatively little is known about the precise reaction mechanism and the associated catalytic cycle.[2,9,10,11]

  • The model reaction studied in this work: Pd-catalyzed alkoxycarbonylation of 1-octene with 13C-PFA, methyl formate, formic acid or phenyl formate in d4-MeOH

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Summary

Introduction

Abstract: “CO-free” carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received widespread attention in homogeneous catalysis lately. The model reaction studied in this work: Pd-catalyzed alkoxycarbonylation of 1-octene with 13C-PFA, methyl formate, formic acid or phenyl formate in d4-MeOH.

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