Transition-metal-catalyzed asymmetric cross-coupling represents a powerful strategy for C-C bond formation and the synthesis of enantiomerically pure molecules. Here, we report a dual nickel/photoredox-catalyzed enantioselective reductive cross-coupling of aryl halides with α-bromobenzoates, readily generated from aliphatic aldehydes, to provide diverse chiral secondary benzylic alcohols that are important motifs in bioactive natural products and pharmaceuticals. This dual catalytic system features mild conditions, good functional group tolerance, broad substrate scope, excellent enantiocontrol, and avoidance of stoichiometric metal reductants, presenting great potential for late-stage functionalization of complex molecules.
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http://dx.doi.org/10.1021/acs.joc.3c02293 | DOI Listing |
RSC Med Chem
December 2024
Modality Platform Technologies, GSK Stevenage SG1 2NY UK
High-throughput chemistry (HTC) and direct-to-biology (D2B) platforms allow for plate-based compound synthesis and biological evaluation of crude mixtures in cellular assays. The rise of these workflows has rapidly accelerated drug-discovery programs in the field of targeted protein degradation (TPD) in recent years by removing a key bottleneck of compound purification. However, the number of chemical transformations amenable to this methodology remain minimal, leading to limitations in the exploration of chemical space using existing library-based approaches.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
Nickel-catalyzed cross-electrophile coupling (XEC) reactions of (hetero)aryl electrophiles represent appealing alternatives to palladium-catalyzed methods for biaryl synthesis, but they often generate significant quantities of homocoupling and/or proto-dehalogenation side products. In this study, an informer library of heteroaryl chloride and aryl bromide coupling partners is used to identify Ni-catalyzed XEC conditions that access high selectivity for the cross-product when using equimolar quantities of the two substrates. Two different catalyst systems are identified that show complementary scope and broad functional-group tolerance, and time-course data suggest that the two methods follow different mechanisms.
View Article and Find Full Text PDFChem Asian J
December 2024
Hybrid Porous Materials Laboratory, Department of Chemistry, Indian Institute of Technology Jammu, Jammu & Kashmir, 181221, India.
Single-atom-based Metal-Organic Frameworks (MOFs) hold great promising candidates for heterogeneous catalysis, demonstrating outstanding catalytic activity and exceptional product selectivity. This is attributed to their optimal atom utilization, high surface energy, and the presence of unsaturated coordination environments. Here in, we have developed a nickel single-atom catalyst (SAC) featuring Ni single atoms covalently attached to defect-engineered Zr-oxide clusters within the stable UiO-66 (Universitetet i Oslo) framework, synthesized via a straightforward solution impregnation method (denoted as UiO-66/Ni now onwards).
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Haihe Laboratory of Sustainable Chemical Transformations, College of Chemistry, Nankai University, Tianjin 300071, China.
ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and a power source, chemists are provided with a system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable of oxidizing or reducing some of the most tenacious compounds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
IISER Kolkata, Chemistry, INDIA.
An established concept to create radical intermediates is photoexcitation of a catalyst to a higher energy intermediate, subsequently leading to a photoinduced electron transfer (PET) with a reaction partner. The known concept of consecutive photoinduced electron transfer (con-PET) leads to catalytically active species even higher in energy by the uptake of two photons. Generally speaking, increased photon uptake leads to a more potent reductant.
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