Recruiting now: Research Associate in Organometallic Chemistry on jobs.ac.uk. Click for details and explore more academic job opportunities on the top job board

The University of Chicago is a private, nondenominational, culturally rich and ethnically diverse coeducational research university located in Hyde Park, Chicago.

We report the synthesis of three chloropnictogenium cations [MSFluindECl]+ (2As, 2Sb and 2 Bi), which unravel different reaction pathways toward Et3SiH, leading to the formation of the neutral arylars...

Reader environment loaded

The reductive aldol reaction is a powerful tool for the regiocontrolled coupling of α,β-unsaturated compounds with aldehydes. The use of stoichiometric organoborane reductants has previously been repo...

Nature - Science publishing giant Elsevier has joined a class action lawsuit against Meta that alleges the reproduction of copyrighted works in developing the Llama AI model.

Functionalization of a sterically encumbered phosphorus precursor enables varied activation pathways for N2O, CO2, and CO. The potasssium phosphanide salt, [K(crypt)][(MsFluInd*)PH] (crypt = 2.2.2.cry...

Antimony-nitrogen interactions yield materials with enhanced stability and the ability to self-heal in aqueous environments

Ring-opening C–N bond cleavage reactions provide an effective means to convert widespread, readily accessible chiral N-heterocycles into hard-to-attain stereodefined linear amines. Current strategies either rely on the strain-induced release of small aziridine and azetidine rings or, for larger ring systems, require highly electrophilic reagents, oxidative conditions, or preinstalled reactive functionalities to enable the ring-opening event. Recently, complementary radical strategies that exploit the reactivity of α-amino-ketyl radicals, formed upon single-electron transfer (SET) reduction of common N-carbonyl protecting groups, have emerged. Nevertheless, these methods facilitate the homolytic fragmentation only of up to 5-membered azacycles. In this study, we leveraged electroreductive conditions to switch the nature of the above C–N bond cleavage manifold from radical to ionic and enable the heterolytic ring-opening of a broad array of unstrained cyclic amines (comprising pyrrolidines, piperidines, azepines, azocanes, and N-macrocycles), protected as N-(thio)amides, carbamates, or ureas. Crucially, this electrochemically enabled reactivity switch grants complementary functional group compatibility and a broader ring size and N-carbonyl group scope. Computational and experimental studies indicate that electrochemical settings are crucial for generating the Mg(II)-Lewis acid catalyst, activating the N-carbonyl moiety while prompting the so-formed oxy-iminium ion intermediates to undergo two consecutive cathodic SET reductions, generating “umpoled” α-amino-α-oxy-carbanion species. These, via irreversible E1cB fragmentation of the adjacent C–N bond, lead to the desired ring-opened products. Our electrochemical procedure can be scaled up and miniaturized (enabling its application to high-throughput experimentation screening), and its synthetic utility has been demonstrated by accessing decorated stereodefined linear amides from stereochemically rich pyrrolidine and azepane derivatives.

These compounds may find uses as nitrene precursors

For over a century, aryldiazonium halides have served as widely used building blocks within synthetic chemistry. They are vital intermediates in converting simple anilines to high-value products, incl...

These compounds may find uses as nitrene precursors

Low oxidation state aluminium complexes have gained wide recognition as discrete and versatile 2-electron reductants, but neutral trimeric structures remain elusive. Here the authors report the synthe...

The isolation of catenated nitrogen compounds is difficult, in part because these chains can readily lose nitrogen, creating a strong thermodynamic push towards decomposition. Now, a series of molecul...

GPE

Zintl clusters have recently emerged as competent catalysts for a variety of organic transformations. Herein, we report the mechanism of functionalized Zintl-cluster-catalyzed hydroboration of pyridin...

The reaction of Zintl phases K3As7 and K3P7 were investigated with 1-azido-4-bromobenzene (4-BrC6H4N3) and found to yield potassium salts of substituted diazadipnictogen rings (general molecular fragm...

The mobility of main-group and transition metal fragments on the surface of a phosphorus cluster, P73–, has been explored using density functional theory. The naked P73– cluster undergoes rapid exchan...

Radical chain initiation strategies are fundamental to the synthesis of small molecule drugs and macromolecular materials. Here a general, thermally driven and scalable method for reductive initiation...

PhD Project - [FSE Bicentenary PhD] New Electrosynthetic Strategies to Nitrile Covalent Warheads, and Their Application to the Development of Electrochemically-Activated Prodrugs for Targeted Drug-De...

Four Oxford University researchers have been selected from over 350 nominations to receive one of the 2025 Philip Leverhulme Prizes. These awards recognise and celebrate the achievements of

Synthesis and Reactivity of Heavy Azadipnictiridines

Small organic rings are important molecular entities that have long played a crucial role in organic synthesis and medicinal chemistry. Similarly, small inorganic rings have shown promise in promoting...

Nitrous oxide (N2O) is sometimes referred to as the forgotten greenhouse gas, but ignoring it would be a mistake. N2O has a greenhouse warming potential 300× that of CO2, and anthropogenic emissions a...