Pyrimidine-Derived Prolinamides as Recoverable Bifunctional Organocatalysts for Enantioselective Inter- and Intramolecular Aldol Reactions under Solvent-Free Conditions

Chiral L-prolinamides 2 containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-pyrimidinyl unit are synthesized and used as general organocatalysts for intermolecular and intramolecular aldol reactions with 1,6-hexanedioic acid as a co-catalyst under solvent-free conditions. The intermolecular reaction between ketone–aldehyde and aldehyde–aldehyde must be performed under wet conditions with catalyst (S,S)-2b at 10 °C, which affords anti-aldols with high regio-, diastereo-, and enantioselectivities. For the Hajos–Parrish–Eder–Sauer–Wiechert reaction, both diastereomers of catalyst 2 give similar results at room temperature in the absence of water to give the corresponding Wieland–Miescher ketone and derivatives. Both types of reactions were scaled up to 1 g, and the organocatalysts were recovered by extractive workup and reused without any appreciable loss in activity. DFT calculations support the stereochemical results of the intermolecular process and the bifunctional role played by the organocatalyst by providing a computational comparison of the H-bonding networks occurring with catalysts 2a and 2b.

The Member States’ Initiatives: An Inter-Institutional Turf War after the Treaty of Lisbon

With the introduction of the Treaty of Lisbon came the possibility for Member States to launch an initiative under the Ordinary Legislative Procedure. This came into being as the scope of co-decision was expanded to cover the more sensitive issues of the third pillar (such as judicial cooperation in criminal matters and police cooperation). It was considered necessary that Member States have a shared right of initiative with the European Commission. One case in which the right of initiative was invoked was the Initiative for a European Protection Order (EPO). This dossier is one of the first and few cases in which the Member States’ Initiative after the Treaty of Lisbon was used. It resulted in a turf war between the Presidency and the Commission regarding the scope of the Member States’ Initiatives. This article looks into the Member States’ Initiative as it was introduced after the Treaty of Lisbon and the debate that took place on the EPO.