Artificial intelligence (AI) and machine learning (ML) are increasingly reshaping experimental chemistry. This review maps the challenges of synthetic organic chemistry to modern digital tools that c...

An anomeric amide-enabled divergent aldehyde functionalization sequence provides one-pot access to unsymmetrical ureas, carbamates, thiocarbamates, thioesters, and amides. Key to this transformation ...

Densely substituted heterocycles are ubiquitous motifs in both natural products and pharmaceuticals. sp3-Heterocycles bearing multiple vicinal stereocenters are especially critical targets due to their challenging construction under precise stereocontrol. The multisubstituted tetrahydrofuran (THF) family, for example, represents a privileged structural motif. Yet, syntheses of THFs are often step-intensive and tailored to a single target structure, as generalized and robust methods that rapidly introduce multiple substituents from simple precursors remain underdeveloped. Herein, we present a distinct approach featuring two core advantages: modular assembly from abundant building blocks, and precise chemo-, regio-, diastereo-, and enantioselectivity. Pivotal to the success of this methodology is synergistic metallaphotoredox–Lewis acid catalysis, which rapidly constructs four bonds in THFs bearing up to four stereocenters. Experimental and computational studies deliver further insight into the mechanism. High-throughput experimentation (HTE) highlights the potential for efficient generation of THF-based libraries.

Densely substituted heterocycles are ubiquitous motifs in both natural products and pharmaceuticals. sp3-Heterocycles bearing multiple vicinal stereocenters are especially critical targets due to thei...

Energy transfer (EnT) catalysed dearomative cycloadditions of bicyclic azaarenes are largely limited to [4+2] pathways, with higher-order cycloadditions being difficult to achieve. Now, the authors ci...

In this study, a mild and selective visible-light-mediated Birch-type reduction of 2-pyridones has been developed. This protocol proved to tolerate a vast number of functional groups, which was achie...

Medium-sized bridged heterocycles are highly attractive structural motifs in bioactive natural products and medicinal chemistry. However, their broader exploration remains limited due to the lack of concise and modular synthetic strategies, as their synthesis is challenged by unfavorable enthalpic and entropic constraints. Herein, we report an energy transfer (EnT)-catalyzed intermolecular (5 + 4) dearomative cycloaddition of furans with vinyl cyclopropanes, providing direct access to (Z)-10-oxabicyclo[5.2.1]deca-3,8-diene scaffolds in a single step. Visible light triplet sensitization unlocks a distinct diene-type 1,4-biradical activation mode in furans. This triplet-state reactivity enables intermolecular higher-order (5 + 4) cycloadditions that remain inaccessible under conventional thermal activation. Mechanistic investigations support an energy transfer pathway and provide insights into the origin of the observed regioselectivity. The resulting partially unsaturated cycloadducts offer multiple synthetic handles for downstream functionalization, enabling rapid and modular incorporation of heterobicyclo[5.2.1]alkane motifs and highlighting their potential as versatile building blocks in synthetic chemistry.

The desire to access molecules with three-dimensional structures is of great importance in drug discovery. Two decades of exploration in selective arene saturation have recently culminated in producti...

Contrary to traditional alkene aziridination via (formal) nitrene transfer, we herein report a strategy that achieves intermolecular aziridination of a single alkene carbon atom and installs an addit...

Saturated, three-dimensional scaffolds are key in modern drug discovery, and highly strained rings serve as privileged building blocks for their synthesis. Now, by tailoring the substitution patterns ...