Selective Hydrofunctionalization of -Allenyl Derivatives with Heteronucleophiles Catalyzed by Brønsted Acids.

In this study, we present a novel and environmentally sustainable protocol for the γ-hydrofunctionalization of -allenyl compounds using various heteronucleophiles catalyzed solely by simple Brønsted acids. The method displays remarkable attributes, highlighting its sustainability, efficiency, regio- and stereoselectivity, as well as its versatile applicability to diverse heteroatom-containing enamides. Notably, our approach eliminates the need for metal catalysts and toxic solvents, representing a significant advancement in greener chemistry practices.

Stereoselective Synthesis of α-Disubstituted β-Homoprolines.

An efficient enantioselective synthesis of chiral α-disubstituted β-homoprolines was developed, starting with the stereodivergent allylation of chiral --butanesulfinyl imines derived from 4-bromobutanal with indium or zinc and using well-established and reliable synthetic transformations. This methodology allows the easy introduction of different substituents at the α-position of the pyrrolidine scaffold and is characterized by the possibility of switching the absolute configuration of the newly formed stereocenter either by changing the configuration of the -butanesufinamide chiral auxiliary or by using a different stereodivergent allylation protocol with the same auxiliary.

Recent Advances in Asymmetric Synthesis of Pyrrolidine-Based Organocatalysts and Their Application: A 15-Year Update.

In 1971, chemists from Hoffmann-La Roche and Schering AG independently discovered a new asymmetric intramolecular aldol reaction catalyzed by the natural amino acid proline, a transformation now known as the Hajos-Parrish-Eder-Sauer-Wiechert reaction. These remarkable results remained forgotten until List and Barbas reported in 2000 that L-proline was also able to catalyze intermolecular aldol reactions with non-negligible enantioselectivities. In the same year, MacMillan reported on asymmetric Diels-Alder cycloadditions which were efficiently catalyzed by imidazolidinones deriving from natural amino acids.

Evaluation of the Pharmacophoric Role of the O-O Bond in Synthetic Antileishmanial Compounds: Comparison between 1,2-Dioxanes and Tetrahydropyrans.

Leishmaniases are neglected diseases that can be treated with a limited drug arsenal; the development of new molecules is therefore a priority. Recent evidence indicates that endoperoxides, including artemisinin and its derivatives, possess antileishmanial activity. Here, 1,2-dioxanes were synthesized with their corresponding tetrahydropyrans lacking the peroxide bridge, to ascertain if this group is a key pharmacophoric requirement for the antileishmanial bioactivity.

A supramolecular bifunctional iridium photoaminocatalyst for the enantioselective alkylation of aldehydes.

The construction of a hybrid metal-organo-photoredox catalyst based on the conjugation of an imidazolidinone organocatalyst and Ir(ppy)2(bipy) (ppy = 2-phenylpyridine, bipy = bipyridine) is described. The introduction of the desired organocatalyst into the bipyridine moiety is quite modular, allowing the preparation of different hybrid photocatalysts, and is realized though a simple click reaction. The hybrid photocatalysts obtained were employed in the benchmark photoredox alkylation of aldehydes.