Ministerial Transposition of EU Directives: Can Oversight Improve Performance?

This paper argues that the extent to which national administrations transpose EU directives in a timely fashion may be related to how transposition is coordinated inside national ministries. Focusing on transposition through secondary legislation in Estonia, Poland and Slovenia, the paper finds initial evidence that oversight can contribute to better transposition performance. Ministries with strong internal oversight tend to be better at timely transposition, while ministries with no or weak oversight perform worse. The results tend to hold if one controls for country effects, party preferences and transposition workload.directives; Estonia; political science

Discovery and development of novel enantioselective C(sp3)-H functionalisations

This thesis describes studies towards new enantioselective C–H activation reactions. In chapter 2 the investigation towards a novel enantioselective cobalt-catalysed C(sp3)–H alkenylation, directed by thioamides, with but-2-ynoates is described. In this method prochiral thioamides undergo asymmetric C(sp3)–H functionalisation with but-2-ynoates in presence of a [Cp*Co(MeCN)3][SbF6]2 complex and chiral carboxylic acid, which allows the formation of chiral thioamides. The method provides alkenylated products as single regioisomers in excellent yields (up to 85%) and high enantiomeric ratios (up to 91:9 er, or up to >99:1 er after single recrystallisation). The protocol is operationally very simple with mild reaction conditions, which is not very common for C–H functionalisations, because the activation of naturally inactive C–H bonds often requires high reaction temperatures. The applicability of this methodology can be found in diverse downstream derivatisations of products, delivering a broad range of enantiopure pharmaceutically and agrochemically relevant scaffolds, such as various substituted heterocycles. Mechanistic investigations and state-of-the-art DFT calculations carried out in collaboration with Ken Yamazaki, Prof Trevor A. Hamlin and Prof F. Matthias Bickelhaupt revealed that the pivotal C–H activation step is rate- and enantiodetermining step. DFT calculations explain the reaction mechanism, and stereochemical outcome of the products, as well as the unusual regioselectivity of the alkenylation reaction. After successfully developing a novel thioamide-directed cobalt-catalysed enantioselective C(sp3)–H alkenylation reaction, in chapter 3 we investigated intramolecular variant of this new reaction. Taking into consideration the specific interactions between a Cp*CoIII complex, thioamides and but-2-ynoates, with suitable substrates the formation of cyclic products should be straightforward, and this project would be a viable follow-up of our completed study

Discovery and development of novel enantioselective C(sp3)-H functionalisations

This thesis describes studies towards new enantioselective C–H activation reactions. In chapter 2 the investigation towards a novel enantioselective cobalt-catalysed C(sp3)–H alkenylation, directed by thioamides, with but-2-ynoates is described. In this method prochiral thioamides undergo asymmetric C(sp3)–H functionalisation with but-2-ynoates in presence of a [Cp*Co(MeCN)3][SbF6]2 complex and chiral carboxylic acid, which allows the formation of chiral thioamides. The method provides alkenylated products as single regioisomers in excellent yields (up to 85%) and high enantiomeric ratios (up to 91:9 er, or up to >99:1 er after single recrystallisation). The protocol is operationally very simple with mild reaction conditions, which is not very common for C–H functionalisations, because the activation of naturally inactive C–H bonds often requires high reaction temperatures. The applicability of this methodology can be found in diverse downstream derivatisations of products, delivering a broad range of enantiopure pharmaceutically and agrochemically relevant scaffolds, such as various substituted heterocycles. Mechanistic investigations and state-of-the-art DFT calculations carried out in collaboration with Ken Yamazaki, Prof Trevor A. Hamlin and Prof F. Matthias Bickelhaupt revealed that the pivotal C–H activation step is rate- and enantiodetermining step. DFT calculations explain the reaction mechanism, and stereochemical outcome of the products, as well as the unusual regioselectivity of the alkenylation reaction. After successfully developing a novel thioamide-directed cobalt-catalysed enantioselective C(sp3)–H alkenylation reaction, in chapter 3 we investigated intramolecular variant of this new reaction. Taking into consideration the specific interactions between a Cp*CoIII complex, thioamides and but-2-ynoates, with suitable substrates the formation of cyclic products should be straightforward, and this project would be a viable follow-up of our completed study.</p

Civil Service Reform in Slovakia and Hungary: road to professionalization?

Civil service reforms in Central and Eastern Europe (CEE). A comparative analysis of Hungary's and Slovakia's civil service systems, especially from the point of view of politicization and professionalization