Rosa López

Planar‐chiral [2.2]paracyclophanes occupy a distinctive position in modern chemistry because their rigid cofacial aromatic architecture connects molecular shape, through‐space electronic communication and chirality within a compact scaffold. These features have made them valuable in asymmetric catalysis, ligand and organocatalyst design, optoelectronic materials and chiroptical systems. However, the preparation of enantioenriched [2.2]paracyclophanes has historically relied on resolution‐based approaches, limiting both efficiency and structural diversification. Catalytic asymmetric synthesis has recently opened new opportunities for the direct construction of planar chirality in [2.2]paracyclophane frameworks, particularly through desymmetrization of prochiral substrates. This Review summarizes recent progress in the catalytic asymmetric synthesis of planar‐chiral [2.2]paracyclophanes, discusses the key structural and mechanistic features underlying enantioinduction, and outlines future directions for this rapidly evolving field. Particular attention is given to how substrate topology, catalyst design and reaction pathway govern stereocontrol, and to how the resulting enantioenriched scaffolds can serve as functional building blocks for catalysis, molecular design and chiral materials.

Chiral triazoles are valuable motifs in catalysis, coordination chemistry, and molecular design, and their incorporation into three-dimensional planar-chiral scaffolds creates compact chiral architectures with well-defined steric and electronic environments. Among such scaffolds, [2.2]paracyclophanes are particularly distinctive, combining configurational stability with through-space interactions. Herein we report the enantioselective CuAAC desymmetrization of challenging and largely unexplored pseudogeminal dialkynyl [2.2]paracyclophanes, affording enantioenriched triazolyl derivatives in high yields with excellent enantioselectivities. The methodology was also extended to pseudopara frameworks.

Planar chirality represents a distinct and underexplored form of molecular asymmetry that arises from restricted three-dimensional conformations. It holds significant potential for expanding chemical space and enabling the development of novel chiral reagents, catalysts, and functional materials. Among the most prominent scaffolds exhibiting planar chirality is the rigid and conformationally stable [2.2]paracyclophane (PCP), known for its exceptional photophysical and electronic properties. In this work, we present a simple, cost-effective, and scalable biocatalytic desymmetrization strategy for the efficient synthesis of two key disubstituted PCP intermediates, the pseudo-geminal and pseudo-para isomers, directly addressing the current lack of catalytic methods for inducing planar chirality on this scaffold. This practical approach enables access to structurally complex PCP frameworks and underscores the largely overlooked potential of biocatalysis as a powerful, sustainable route to planar chiral molecules.

Ru-sensitized [2+2]-photocycloaddition of oxazolones 1 in presence of BF ₃ gives selectively the δ-1,2-diaminotruxinic acids 2. Heating of 2 with NaOMe promotes an unprecedented cyclobutane ring expansion, giving the highly substituted pyrrolidines 3.

Planar chirality is one of the most fascinating expressions of chirality, which is exploited by nature to lock three‐dimensional chiral conformations and, more recently, by chemists to create new chiral reagents, catalysts, and functional organic materials. Nevertheless, the shortage of procedures able to induce and secure asymmetry during the generation of these unique chiral entities has dissuaded chemists from exploiting their structural properties. This Minireview intends to illustrate the limited but remarkable catalytic methods that have been reported for the production of planar chirality in strained molecules and serve as a source of inspiration for the development of new unconventional procedures, which are expected to appear in the near future.

Planar chirality is one of the most fascinating expressions of chirality, which is exploited by nature to lock three‐dimensional chiral conformations and, more recently, by chemists to create new chiral reagents, catalysts, and functional organic materials. Nevertheless, the shortage of procedures able to induce and secure asymmetry during the generation of these unique chiral entities has dissuaded chemists from exploiting their structural properties. This Minireview intends to illustrate the limited but remarkable catalytic methods that have been reported for the production of planar chirality in strained molecules and serve as a source of inspiration for the development of new unconventional procedures, which are expected to appear in the near future.

N,N‐Diacylaminals are flexible molecular scaffolds that have commonly been utilized as amide surrogates in peptidomimetics. The singularities of this motif as an N‐acyl imine equivalent and as hydrogen‐bond donor have recently opened new synthetic opportunities, especially in the field of asymmetric catalysis. This concept article highlights this diverse synthetic potential and provides the elements necessary for further developments.

The potential of β‐alkoxy α‐keto amides as pronucleophiles in the enantioselective Mannich type reaction with p‐nosyl imines is presented. The proper combination of β‐alkoxy α‐keto amides and a squaramide‐based Brønsted base catalyst produced highly enantioenriched Mannich adducts, which may be transformed into functionalized amino diols.