Hydride Route for the Palladium-Catalysed Cyclocarbonylation of Monoterpenes

This paper focuses on the mechanism by which a monoterpene undergoes a cyclocarbonylation reaction catalysed by a palladium complex. Evidence is provided, based on intermediate species observed under pressure or with various ligands, that the catalytic cycle follows a hydride route starting from [Pd(H)(SnCl3)L2]. The [Pd(H)(SnCl3)L2] complexes (L = PPh3 or PCy3) have been observed for the first time by multinuclear NMR spectroscopy. Cationic hydride complexes or palladium(0) precursors show either no or poor reactivity. Studies related to model platinum complex chemistry have detected an acylplatinum species. Most of the observations have been done on the cyclocarbonylation of isopulegol, dihydromyrcenol or isolimonene into the corresponding lactones or cyclopentanones. The use of dihydromyrcene allowed us to observe the acylplatinum complex and the corresponding elusive acylpalladium species. The co‐catalytic role of SnCl2 is also demonstrated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)