David Virieux

A catalytic intramolecular aza‐Wittig reaction of azide‐functionalized imides has been developed under P ^III /P ^V redox organocatalytic conditions, enabling rapid and direct access to structurally diverse amidine‐containing heterocycles. The transformation is promoted by a methanophosphocine oxide catalyst in combination with phenylsilane as the reductant and bis(4‐nitrophenyl) phosphate (BNPA) as a Brønsted acid additive. Under mild, metal‐free conditions (2 mol% catalyst, 5 mol% additive), a broad spectrum of imides undergoes efficient cyclization to furnish fused nitrogen heterocycles in yields up to 96%. The method displays broad functional‐group tolerance, including halogenated, alkyl‐substituted, and structurally complex substrates, such as thalidomide derivatives, and enables access to a wide range of privileged amidine scaffolds. Its synthetic utility is further highlighted through concise applications to quinazolinone precursor synthesis and the antitumor agent batracylin. This work expands the scope of P ^III /P ^V redox organocatalysis and provides a practical and sustainable catalytic alternative to classical stoichiometric phosphine‐mediated aza‐Wittig reactions.

A new class of modular phosphine–oxazoline ligands (Indol-PHOX) has been developed and successfully applied in Pd-catalyzed enantioselective decarboxylative allylation to access valuable α-allyl-α-fluoro ketones with yields up to 99% and 96% ee.

This study focuses on the synthesis, properties, and comparative analysis of new flame-retardant compounds: coumarins and isophosphinolines. These compounds feature a diarylphosphine oxide (DAPO) substituent at the β-position relative to both the carbonyl and the phosphoryl groups. Various derivatives with halogens, phosphorus, and/or aromatics substituents were synthetized and their thermal stability and flammability were evaluated at the microscale by thermogravimetric analysis (TGA) and pyrolysis–combustion flow calorimetry (PCFC) in order to identify the most promising molecules for use as flame-retardant (FR) additives or comonomers. FTIR-coupled PCFC analysis was also carried out to study the combustion profiles of the molecules. Beyond the confirmation of some expected trends, such as the char promotion of phosphorus and flame inhibition of halogens, the study revealed some unexpected findings that warrant further investigation. These include the prominent role of the chlorine substitution position on the aromatic ring, as well as significant differences in FR performance between diastereoisomers.

A novel Ru‐catalyzed asymmetric transfer hydrogenation (ATH) strategy has been developed for the efficient synthesis of valuable chiral α‐aminophosphonates from readily available α‐iminophosphonates. This method enables the conversion of both acyclic and cyclic substrates in high yields (up to 97%) and excellent enantioselectivities (up to >99:1), providing a practical entry to phosphorus‐containing chiral amines. Notably, this is the first reported application of ATH to α‐iminophosphonates, offering a robust and operationally convenient alternative to conventional asymmetric hydrogenation (AH) approaches.

A general and effective (3 + 2) cycloaddition reaction between nitrones and allenes to synthesize fluoro‐phosphonopyrrolidin‐3‐ones, as well as spiropyrrolidin‐3‐one phosphonates is reported under microwave heating. The products have been isolated in moderate to good yields and exclusively as 4,5‐trans diastereoisomers in all transformations.

C-H activation is a powerful strategy for forming C-C bonds without the need for prefunctionalization. In this paper, we present a general, direct, and regioselective palladium-catalyzed functionalization of a phosphorus heterocycle, 2-phenyl-1H-isophosphinoline 2-oxide. The mild reaction conditions enabled the introduction of various functionalized alkenes. Moreover, the flame-retardant properties of selected products clearly highlighted the synergy between the phosphine oxide and another heteroatom-based group, even in the condensed phase.

The study of chemical constituents is an essential element in the valorization of medicinal plants, which can be used to treat a number of pathologies. This work aims to contribute to a better understanding of the chemical composition of Paullinia pinnata (Sapindaceae), a medicinal plant used in Côte d'Ivoire for the traditional treatment of cardiovascular diseases. This study explores the relationship between the compounds identified in this plant and its use in cardiovascular disease treatment. Extraction methods (solid/liquid and liquid/liquid) and identification by GC-MS and HPLC-ESI-QTOF-MS analyses were used. The GC-MS analysis of the various extracts (hexane, dichloromethane and ethyl acetate) identified 32 compounds consisting of steroids, triterpenes, fatty acids, alkaloids and phenolic compounds. HPLC-ESI-QTOF-MS analysis of these extracted memes identified 21 phenolic compounds. In total 53 compounds were identified with the two analytical methods used. These molecules identified are: palmitic acid, 9-(E)-octadecenoic acid, stigmasterol, β-Sitosterol, umbelliferone, epicatechin quinone, clemiscosin A, caffeic acid, catechin, epicatechin and O-β-D-glucopyranosyloxy-4-methyl-2 (5 H)-furanone, cinnamtannin B-2; cinnamtannin B1, procyanidin B2, epicatechin quinone, clemiscosin C, clemiscosin A, kaempferide and epicatechin. These compounds have been identified for their antioxidant, anti-free radical, cardiotonic, neuroprotective and anti-inflammatory properties. The presence of these compounds could justify the use of Paullinia pinnata in the traditional treatment of cardiovascular diseases.

Owing to their role in drug design and as building blocks, enantiopure α‐hydroxyphosphonates stand at the forefront of contemporary research. In recent decades, synthetic methods have been developed highlighting the obvious interest and practical importance of these compounds. This review aims to provide an up‐to‐date overview of the synthesis of chiral α hydroxyphosphonates covering the literature from its inception in 1983 to February 2024.

Asymmetric transfer hydrogenation (ATH) is arguably one of the most powerful tools for the synthesis of chiral compounds. Despite tremendous advances in this field, the reduction of α-ketophosphonates remains largely unexplored. Herein, we report an efficient Ru-catalyzed ATH on a broad range of α-ketophosphonates. Compared with existing methods, our approach offers as advantages mild conditions, operational simplicity, limited waste generation, broad substrate scope (26 examples), good to excellent yields (75-93%), and excellent levels of stereoinduction (from 90% to >99% ee).