Amino alcohols, cyclopropanes and nitriles are privileged structural motifs found in the scaffold of natural products and bioactive compounds. In addition, they are versatile building blocks in organic chemistry. The development of new and increasingly efficient synthetic methods to access these chemical motifs from readily available feedstocks is therefore highly desirable. In this context, alkenes have been substrates of choice to rapidly access complex molecules, as two new functionalities can be installed across their double bond. To achieve such transformations, palladium catalysis and radical chemistry stand as two of the most efficient strategies. In this thesis, a new palladium-catalyzed carboamination of allylic alcohols using a trifluoroacetaldehyde-based tether was first investigated. The tether could be easily installed on diverse allylic alcohol substrates, the formed hemiaminals underwent in high yield and diastereoselectivities the desired transformation under optimized conditions. Both alkynyl- and aryl-bromides could be used as electrophilic partners in the reaction. For the latter, in order to supress a competitive Heck-pathway, a new phosphine-based ligand âFuXPhosâ had to be developped and was key to reach high yields for the aminoarylation in combination with CsOTf as additive. The tether in the obtained products could be cleaved under acidic conditions delivering valuable amino alcohol derivatives. This difunctionalization strategy mediated by palladium was then applied to the strained alkene of cyclopropenes. While preliminary results for the intramolecular carbo-amination and carbo-etherification of cyclopropenes could be obtained, the difficulty to access the starting materials for these transformations led to consider a more convergent approach to access functionalized cyclopropanes. Using radical chemistry, a novel synthesis of bicyclo[3.1.0]hexanes could be developed, by a (3+2) annulation of cyclopropylanilines with cyclopropenes mediated by photoredox. The scope of the transformation was broad for both reaction partners, but the products were obtained with low diastereoselectivities. It was found that by combining difluorocyclopropenes with a bulky aromatic N-substituent on the cyclopropylamine, the corresponding fluorinated bicyclo[3.1.0]hexanes could be accessed in good yields and diastereoselectivities under slightly re-optimized conditions. Finally, the possibility to achieve an amination reaction of cyclopropenes using N-centered radicals was investigated. It was discovered that the addition of azidyl radicals to the double bond of cyclopropenes under photoredox conditions led to the formation of two new products coming from an unexpected ring cleavage: an alkenyl nitrile and a quinoline. While the formation of the quinoline product could not be optimized above 47% yield, conditions could be found for the selective formation of the alkenyl nitrile in high yields using cheap and commercial reagents. Through the scope investigations it was discovered that an aryl-substituent on the double bond of the cyclopropene substrates was necessary for the transformation to proceed. Despite this limitation various substrates could be engaged in the transformation and delivered the corresponding alkenyl nitriles in high yields. With 1,2-diaryl substituted cyclopropenes a synthesis of valuable polycyclic aromatic compounds could be developed, through a one pot radical amination / oxidative cyclization.