La tesis doctoral está dividida en una introducción general y cuatro capítulos. En la introducción general, se describen diferentes productos naturales y derivados sintéticos que contienen un núcleo de oxindol en su estructura junto a comentarios sobre sus actividades biológicas. Además, también están incluidas diversas metodologías de síntesis para la síntesis de estos derivados de oxindol junto a una explicación general sobre el proceso de alquilación desacetilativa. Los capítulos se han desarrollado con una breve introducción, una propuesta de objetivos, comentarios y discusión de los resultados obtenidos en las investigaciones finalizando con las conclusiones obtenidas. El Capítulo 1 trata sobre la síntesis de 2-oxindoles 3,3-disustitutidos a través de un proceso de alquilación desacetilativa utilizando halogenuros de alquilo. El Capítulo 2 describe la alilación y la alilación desacetilativa catalizada por paladio de los derivados de 2-oxindol utilizando alcoholes alílicos no activados. En el Capítulo 3 está incluida la síntesis de 3-fluoro-2-oxindoles combinando las metodologías descritas en los dos anteriores capítulos. Finalmente, en el Capítulo 4, se desarrolla la alquilación fotocatalizada de olefinas electrofílicas a través de sulfinatos de zinc bencílicos y alquílicos.

Palladium-catalyzed reactions have found widespread use in contemporary organic chemistry due to their impressive range of functional group tolerance and high chemo- and regioselectivity. The pioneering contributions to the development of the Pd-catalyzed C-C bond forming cross-coupling reaction were rewarded with the Nobel Prize in Chemistry in 2010. Today, this is a rapidly growing field, and the development of novel methods, as well as the theoretical understanding of the various processes involved are of immense importance for continued progress in this field. The aim of the work presented in this thesis was to develop novel palladium(0)- and palladium(II)-catalyzed reactions. The work involved in achieving this aim led to the development of a Mo(CO)6-mediated carbonylative Stille cross coupling reaction for the preparation of various deoxybenzoins. The protocol utilized convenient gas-free conditions to facilitate the carbonylative coupling of benzyl bromides and chlorides with aryl and heteroaryl stannanes. Mo(CO)6-assisted conditions were then used in the development of a general protocol suitable for the aminocarbonylation of aryl triflates. Both electron-poor and electron-rich triflates were coupled with primary, secondary and aryl amines. In addition, DMAP was found to be a beneficial additive when using sterically hindered or poorly nucleophilic amines. An efficient and convenient method for the synthesis of styrenes from arylboranes was developed, employing the relatively inexpensive vinyl acetate as the ethene source under Pd(II)-catalyzed conditions. The reaction mechanism was studied using ESI-MS, and a plausible catalytic cycle was proposed. A method for the oxidative Heck reaction employing aryltrifluoroborates and aryl MIDA boronates was also developed. Electron-rich and electron-poor olefins were regioselectively arylated under microwave-assisted conditions. Various arylboron species were identified in an ongoing reaction using ESI-MS.    Further investigations led to the development of a direct method for the synthesis of arylamidines from aryltrifluoroborates and cyanamides. Under Pd(II)-catalyzed conditions it was possible to insert the aryl into primary, secondary and tertiary cyanamides. Finally, a desulfitative method for the synthesis of aryl ketones was developed. A variety of aryl sulfinates were effectively inserted into alkyl- and aryl nitriles. The mechanism was further investigated using ESI-MS and a plausible catalytic cycle was proposed.