Direct borylation of C-H bonds is a privileged strategy to access versatile building blocks and valuable derivatives of complex molecules (late-stage functionalization, metabolite synthesis). This perspective aims to provide an overview and classification of the catalytic systems developed in this fast-growing area of research. Unexpected selectivity differences between two established directed-borylation systems have been discovered using high-throughput experimentation highlighting the importance of classical control experiments in catalysis research.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.2533/chimia.2024.513 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Theoretical Insight into the Multiple Roles of the Silyl-Phenanthroline Ligand in Ir-Catalyzed C(sp)-H Borylation.
J Org Chem
December 2024
State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China.
Silyl-phenanthroline (NN'Si) ligand ancillary iridium-catalyzed C(sp)-H borylation is investigated theoretically. Density functional theory calculations clearly disclose that the (NN'Si)Ir(H)(Bpin) (NN'Si = 6-[(di--butylsilyl)methyl]-1,10-phenanthroline) complex is a resting state, and the (NN'Si)Ir(Bpin) complex serves as an active species in the catalytic cycle. The remarkably high activity of this type of a catalyst arises from the rapid reductive elimination of HBpin from (NN'Si)Ir(H)(Bpin) to generate the active species (NN'Si)Ir(Bpin).
View Article and Find Full Text PDFDesign and Synthesis of Sulfur-Containing Tetradentate Ligands for Ir-Catalyzed Asymmetric Hydrogenation of Ketones.
Org Lett
October 2024
Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Department of Chemistry and Medi-X Pingshan, Southern University of Science and Technology, Shenzhen 518055, People's Republic of China.
Developing highly active and enantioselective ligands for the asymmetric hydrogenation of ketones has consistently attracted significant attention from scientists. A series of novel tetradentate sulfur-containing ligands, termed as f-thiophamidol, were successfully designed and synthesized which exhibited excellent performance in the asymmetric hydrogenation of simple ketones (up to 99% yield, 99% ee) and α-substituted β-keto sulfonamides (up to 99% yield, 99% ee, 99:1 dr). The subsequent successful gram-scale experiments with high TON demonstrated the immense potential application value of this system in synthesizing drug molecules.
View Article and Find Full Text PDFThe Difference in Ir-Catalyzed C(sp)-H and C(sp)-H Bond Activation Assisted by a Directing Group: Cyclometalation via - or -Chelation?
Inorg Chem
September 2024
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130012, China.
Iridium-catalyzed C-H borylation of aromatic and aliphatic hydrocarbons assisted by a directing group was theoretically investigated. Density functional theory (DFT) calculations revealed both Ir-catalyzed C(sp)-H and C(sp)-H borylations via an Ir/Ir catalytic cycle, where the tetra-coordinated (C, N)Ir(Bpin) complex with two vacant sites is an active species. Dramatically, the orientation of cyclometalation for C(sp)-H bond activation assisted by a directing group is different from the C(sp)-H one.
View Article and Find Full Text PDFDo we really need ligands in Ir-catalyzed C-H borylation?
Chimia (Aarau)
August 2024
Research Chemistry, Syngenta Crop Protection AG, Schaffhauserstrasse 101, Stein AG CH-4332, Switzerland.
Direct borylation of C-H bonds is a privileged strategy to access versatile building blocks and valuable derivatives of complex molecules (late-stage functionalization, metabolite synthesis). This perspective aims to provide an overview and classification of the catalytic systems developed in this fast-growing area of research. Unexpected selectivity differences between two established directed-borylation systems have been discovered using high-throughput experimentation highlighting the importance of classical control experiments in catalysis research.
View Article and Find Full Text PDFComputational Design of Ligands for the Ir-Catalyzed C5-Borylation of Indoles through Tuning Dispersion Interactions.
J Am Chem Soc
September 2024
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
The indole moiety is ubiquitous in natural products and pharmaceuticals. C-H borylation of the benzenoid moiety of indoles is a challenging task, especially at the C5 position. We have combined computational and experimental studies to introduce multiple noncovalent interactions, especially dispersion, between the substrate and catalytic ligand to realize C5-borylation of indoles with high reactivity and selectivity.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!