Chiral Ionic Liquids Based on L-Cysteine Derivatives for Asymmetric Aldol Reaction

Structure, and consequently properties, of ionic liquids can be easily tailored by changing cation/anion combinations and/or attaching functional groups. By grafting enantiopure moieties to the framework of ionic liquid it is possible to prepare bioinspired chiral molecules that can serve as a reaction medium, additive or even asymmetric catalyst. In this context, new chiral ionic liquids (CILs), based on biomolecules, such as aminoacids (L-cysteine derivatives), have been synthesised and tested in asymmetric aldol condensation of aldehydes and ketones. The best results were obtained for CILs composed of S-methyl-L-cysteine cation and bis(trifluoromethane)sulfonimide anion, in the reaction of 2- or 4-nitrobenzaldehyde with acetone or cyclohexanone, giving the aldol product in moderate yields 70–76% and high ee values (up to 96%).

Planar-Chiral P and N-bridged Diferrocenes

We describe the synthesis of planar-chiral diferrocene compounds 4, 7 and 12, intended as key precursors for a new family of asymmetric catalyst ligands with less complex structures than their popular equivalents. In contrast to conventional 1,2-disubstituted ferrocenes containing center-chiral and planar-chiral elements, these compounds are purely planar-chiral due to the absence of α-substiuted ethyl groups. The title compounds 4, 7 and 12 were obtained from known precursors in 87%, 59% and 60% yields, respectively.

A homochiral vanadium–salen based cadmium bpdc MOF with permanent porosity as an asymmetric catalyst in solvent-free cyanosilylation

This chiral framework shows the highest H2 adsorption and CO2 capacity for currently known salen-based MOFs and shows an excellent performance as an asymmetric catalyst in solvent-free cyanosilylation.

A catalytic chiral gel microfluidic reactor assembled via dynamic covalent chemistry

A novel dynamic covalent gel strategy is reported to immobilize an asymmetric catalyst within the channels of a microfluidic flow reactor.

Redox-configurable ambidextrous catalysis: structural and mechanistic insight

A helically chiral copper complex is used as a switchable asymmetric catalyst capable of delivering either enantiomer of a Michael addition reaction.

Asymmetric Lewis acid catalysis directed by octahedral rhodium centrochirality

A chiral-at-metal octahedral rhodium(iii) complex serves as an effective asymmetric catalyst for Michael additions (electrophile activation) and α-aminations (nucleophile activation).