The Tishchenko reaction mediated by organo-f-complexes: the myths and obstacles.

For over a century, the Tishchenko reaction has been a valuable technique for synthesizing esters from aldehydes, serving a variety of applications in different domains. Beyond the remarkable advances in organoactinide and organolanthanide chemistry over the past two decades, there has been a significant increase in the research of the electrophilic d0/fn chemistry of organoactinide and organolanthanide compounds due to the captivating interplay between their structure and reactivity, and their exceptional performance in various homogeneous catalytic processes. The remarkable influence of ligand design, both in terms of steric hindrance and electronic properties, on the catalytic activity of organo-f-element complexes in organic transformations is well-established. However, the traditional view was that the significant oxophilicity of actinide and lanthanide complexes makes them unfavorable for reactions involving oxygen because of catalytic poisoning and their applications have been relatively limited, primarily focused on hydroalkoxylation, small-molecule activation, and cyclic ester polymerization. This review dissects the intricate interplay between ligand design and catalytic activity in actinide and lanthanide complexes, specifically in the context of the Tishchenko esterification.

N-Heterocyclic imino-catalyzed 1,4-regioselective azide-alkyne cycloaddition (AAC): a metal-free approach.

An unprecedented synthetic approach has been devised to efficiently synthesize regioselective 1,4-disubstituted 1,2,3-triazoles. This technique relies on the use of innovative metal-free highly basic N-heterocyclic imino catalysts. The experimental observations have been supported further by TD-DFT computational studies.