Photoredox Catalyzed Site-Selective Generation of Carbanions from C(sp3)-H bonds in Amines

The selective activation of sp3 carbon-hydrogen bonds in presence of multiple C¬-H bonds is challenging and remains of supreme importance in chemical research. Herein, we describe the activation of a C(sp3) H bond in α position to an amine via a carbanion intermediate. In the presence of several α amine sites, only one specific position is selectively activated. Applying this protocol, the proposed carbanion intermediate was effectively trapped with different electrophiles such as deuterium (D+), tritium (T+), or carbonyl compounds compiling over 50 examples. Further, this methodology was used to install deuterium or tritium in different drug derivatives (> 10 drugs) at a selected position in a late-stage functionalization. In addition, the protocol is suitable for a gram-scale synthesis and a detailed mechanistic investigation has been carried out to support our hypothesis.

Confinement of Au3+-Rich Clusters by Silicalite-1 for Selective Solvent-Free Oxidation of Toluene

Selective oxidation of the primary carbon-hydrogen bonds in the methyl group of toluene to corresponding oxygenates is of immense significance. This transformation, however, remains challenging and often requires either extensive...

Photo-initiated oxidation of C–H bonds by diimine complexes of vanadium(v)

The photochemical activation of carbon–hydrogen bonds by vanadium(v)–dioxo and vanadium(v)–oxo–peroxo diimine complexes is described.

Reaction of H2 with mitochondria-relevant metabolites using a multifunctional molecular catalyst

The Krebs cycle is the fuel/energy source for cellular activity and therefore of paramount importance for oxygen-based life. The cycle occurs in the mitochondrial matrix, where it produces and transfers electrons to generate energy-rich NADH and FADH2, as well as C4-, C5-, and C6-polycarboxylic acids as energy-poor metabolites. These metabolites are biorenewable resources that represent potential sustainable carbon feedstocks, provided that carbon-hydrogen bonds are restored to these molecules. In the present study, these polycarboxylic acids and other mitochondria-relevant metabolites underwent dehydration (alcohol-to-olefin and/or dehydrative cyclization) and reduction (hydrogenation and hydrogenolysis) to diols or triols upon reaction with H2, catalyzed by sterically confined iridium–bipyridyl complexes. The investigation of these single–metal site catalysts provides valuable molecular insights into the development of molecular technologies for the reduction and dehydration of highly functionalized carbon resources.

Reaction of H2 with Mitochondria-Relevant Metabolites Using a Multifunctional Molecular Catalyst

The Krebs cycle is the fuel/energy source for cellular activity, and therefore of paramount importance for oxygen-based life. The cycle occurs in the mitochondrial matrix, where it produces and transfers electrons to generate energy-rich NADH and FADH₂, as well as C₄-, C₅-, and C₆-polycarboxylic acids as energy-poor metabolites. These metabolites are bio-renewable resources that represent potential sustainable carbon feedstocks, provided that carbon–hydrogen bonds are restored to these molecules. In the present study, polycarboxylic acids of the Krebs cycle and other mitochondria-relevant metabolites are dehydrated and reduced to diols or triols upon reaction with H₂, catalyzed by sterically confined iridium-bipyridyl complexes.

Reaction of H2 with Mitochondria-Relevant Metabolites Using a Multifunctional Molecular Catalyst

The Krebs cycle is the fuel/energy source for cellular activity, and therefore of paramount importance for oxygen-based life. The cycle occurs in the mitochondrial matrix, where it produces and transfers electrons to generate energy-rich NADH and FADH₂, as well as C₄-, C₅-, and C₆-polycarboxylic acids as energy-poor metabolites. These metabolites are bio-renewable resources that represent potential sustainable carbon feedstocks, provided that carbon–hydrogen bonds are restored to these molecules. In the present study, polycarboxylic acids of the Krebs cycle and other mitochondria-relevant metabolites are dehydrated and reduced to diols or triols upon reaction with H₂, catalyzed by sterically confined iridium-bipyridyl complexes.