The chemical inertness of abundant and commercially available alkyl chlorides precludes their widespread use as reactants in chemical transformations. Presented in this work is a metallaphotoredox methodology to achieve the catalytic intramolecular reductive cyclization of unactivated alkyl chlorides with tethered alkenes. The cleavage of strong C(sp³)−Cl bonds is mediated by a highly nucleophilic low‐valent cobalt or nickel intermediate generated by visible‐light photoredox reduction employing a copper photosensitizer. The high basicity and multidentate nature of the ligands are key to obtaining efficient metal catalysts for the functionalization of unactivated alkyl chlorides.

The cooperative action between the CsPbBr ₃ surface and capping makes the photoredox homo-/cross-coupling of benzyl bromides under mild conditions possible.

Self-driving laboratories have the potential to revolutionize chemical discovery and optimization, yet their widespread adoption remains limited by high costs, complex infrastructure and limited accessibility. Here we introduce RoboChem-Flex, a low-cost, modular self-driving laboratory platform designed to democratize autonomous chemical experimentation. The system combines customizable, in-house-built hardware with a flexible Python-based software framework that integrates real-time device control and advanced Bayesian optimization strategies, including multi-objective and transfer learning workflows. RoboChem-Flex supports both fully autonomous closed-loop operation and human-in-the-loop configurations, enabling seamless integration with shared analytical equipment and minimizing entry barriers. We validate the versatility of the platform across six diverse case studies, including photocatalysis, biocatalysis, thermal cross-couplings and enantioselective catalysis, spanning both single- and multi-objective optimizations. Through these case studies, we demonstrate RoboChem-Flex’s ability to navigate large, complex chemical spaces, autonomously identify scalable high-performance reaction conditions, and flexibly adapt to a variety of analytical set-ups. By providing an affordable, scalable and open platform, RoboChem-Flex offers a tangible step towards making self-driving laboratories accessible to resource-limited laboratories, fostering broader participation in automated chemical research.

A modular, automated photoreactor system for CO ₂ hydrogenation enables precise conversion into methane or carbon monoxide. The carbon monoxide is subsequently utilized in carbonylation reactions, advancing sustainable synthesis and CO ₂ utilization.

The screening of a family of complexes of the formula [RuCl₂(R-pybox)(L)] (R-pybox = Ph-, ⁱPr- or indane-pybox; L = monodentate P, N or C ligand) in the enantioselective hydrogenation of N-aryl imines indicates a strong influence of the R-pybox substituents and the L ligand in the process. A comparison indicates that the best results are obtained with the complex [RuCl₂(Ph-pybox)(PPh(OMe)₂)] which provided values of 99% ee for the reduction of several imines derived from aryl alkyl ketones. It is worth noting that this complex is capable of reducing the mentioned imines under transfer hydrogenation conditions using isopropanol as a hydrogen donor with equally high enantioselectivities.

The chemical inertness of abundant and commercially available alkyl chlorides precludes their widespread use as reactants in chemical transformations. Presented in this work is a metallaphotoredox methodology to achieve the catalytic intramolecular reductive cyclization of unactivated alkyl chlorides with tethered alkenes. The cleavage of strong C(sp³)−Cl bonds is mediated by a highly nucleophilic low‐valent cobalt or nickel intermediate generated by visible‐light photoredox reduction employing a copper photosensitizer. The high basicity and multidentate nature of the ligands are key to obtaining efficient metal catalysts for the functionalization of unactivated alkyl chlorides.