Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Access to C(sp³) borylated and silylated cyclic molecules: hydrogenation of corresponding arenes and heteroarenes.

ABSTRACT: This paper presents a simple and cost-effective hydrogenation method for synthesizing a myriad of cycloalkanes and saturated heterocycles bearing boryl or silyl substituents. The catalyst used are heterogeneous, readily available, bench stable, and recyclable. Also demonstrated is the application of the method to compounds that possess both boryl and silyl groups. When combined with Ir-catalyzed sp² C-H borylation, such hydrogenations offer a two-step complementary alternative to direct sp³ C-H borylations that can suffer selectivity and reactivity issues. Of practical value to the community, complete stereochemical analyses of reported borylated compounds that were never fully characterized are reported herein.

SUBMITTER: Chhabra A

PROVIDER: S-EPMC10985595 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Access to C(sp<sup>3</sup>) borylated and silylated cyclic molecules: hydrogenation of corresponding arenes and heteroarenes.

Chhabra Arzoo A Reich Sabrina S Shannon Timothy M TM Maleczka Robert E RE Smith Milton R MR

RSC advances 20240301 15

This paper presents a simple and cost-effective hydrogenation method for synthesizing a myriad of cycloalkanes and saturated heterocycles bearing boryl or silyl substituents. The catalyst used are heterogeneous, readily available, bench stable, and recyclable. Also demonstrated is the application of the method to compounds that possess both boryl and silyl groups. When combined with Ir-catalyzed sp<sup>2</sup> C-H borylation, such hydrogenations offer a two-step complementary alternative to dire ...[more]

PMID: 38567346

Similar Datasets

Catalytic Transfer Hydrogenation of Arenes and Heteroarenes.

Project description:Transfer hydrogenation reactions are of great interest to reduce diverse molecules under mild reaction conditions. To date, this type of reaction has only been successfully applied to alkenes, alkynes and polarized unsaturated compounds such as ketones, imines, pyridines, etc. The reduction of benzene derivatives by transfer hydrogenation has never been described, which is likely due to the high energy barrier required to dearomatize these compounds. In this context, we have developed a catalytic transfer hydrogenation reaction for the reduction of benzene derivatives and heteroarenes to form complex 3-dimensional scaffolds bearing various functional groups at room temperature without needing compressed hydrogen gas.

| S-EPMC7702167 | biostudies-literature

Chemoselective hydrogenation of heteroarenes and arenes by Pd-Ru-PVP under mild conditions.

Project description:Monometallic (Pd, Ru or Rh) and bimetallic (Pd0.5-Ru0.5) alloy NPs catalysts were examined for the hydrogenation of quinoline. Pd-Ru alloy catalyst showed superior catalytic activity to the traditional Rh catalyst. The characterization of Pd0.5-Ru0.5 catalysts, HAADF-EDX mapping and XPS analysis suggested that the alloy state of PdRu catalysts remained unchanged in the recovered catalyst. Furthermore, the catalyst was highly selective for the hydrogenation of different arenes.

| S-EPMC9058507 | biostudies-literature

Iridium-Catalysed Transfer Hydrogenation of 1,8-Naphthyridine with Indoline: Access to Functionalized N-Heteroarenes

Project description: Not available

| S-EPMC10707882 | biostudies-literature

Catalytic radical difluoromethoxylation of arenes and heteroarenes.

Project description:Intermolecular C-H difluoromethoxylation of (hetero)arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a redox-active difluoromethoxylating reagent 1a and photoredox catalysts for the direct C-H difluoromethoxylation of (hetero)arenes. Our approach is operationally simple, proceeds at room temperature, and uses bench-stable reagents. Its synthetic utility is highlighted by mild reaction conditions that tolerate a wide variety of functional groups and biorelevant molecules. Experimental and computational studies suggest single electron transfer (SET) from excited photoredox catalysts to 1a forming a neutral radical intermediate that liberates the OCF2H radical exclusively. Addition of this radical to (hetero)arenes gives difluoromethoxylated cyclohexadienyl radicals that are oxidized and deprotonated to afford the products of difluoromethoxylation.

| S-EPMC6429774 | biostudies-literature

Catalytic C-H Trifluoromethoxylation of Arenes and Heteroarenes.

Project description:The intermolecular C-H trifluoromethoxylation of arenes remains a long-standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a novel trifluoromethoxylating reagent and redox-active catalysts for the direct (hetero)aryl C-H trifluoromethoxylation. Our approach is operationally simple, proceeds at room temperature, uses easy-to-handle reagents, requires only 0.03?mol?% of redox-active catalysts, does not need specialized reaction apparatus, and tolerates a wide variety of functional groups and complex structures such as sugars and natural product derivatives. Importantly, both ground-state and photoexcited redox-active catalysts are effective. Detailed computational and experimental studies suggest a unique reaction pathway where photoexcitation of the trifluoromethoxylating reagent releases the OCF3 radical that is trapped by (hetero)arenes. The resulting cyclohexadienyl radicals are oxidized by redox-active catalysts and deprotonated to form the desired products of trifluoromethoxylation.

| S-EPMC6105550 | biostudies-literature

Photocatalytic trifluoromethoxylation of arenes and heteroarenes in continuous-flow.

Project description:The first example of photocatalytic trifluoromethoxylation of arenes and heteroarenes under continuous-flow conditions is described. Application of continuous-flow microreactor technology allowed to reduce the residence time up to 16 times in comparison to the batch procedure, while achieving similar or higher yields. In addition, the use of inorganic bases was demonstrated to increase the reaction yield under batch conditions.

| S-EPMC7308607 | biostudies-literature

Ligand-free nickel catalyzed perfluoroalkylation of arenes and heteroarenes.

Project description:We describe a "ligand-free" Ni-catalyzed perfluoroalkylation of heteroarenes to produce a diverse array of trfiluoromethyl, pentafluoroethyl and heptafluoropropyl adducts. Catalysis proceeds at room temperature via a radical pathway. The catalytic protocol is distinguished by its simplicity, and its wide scope demonstrates the potential in the late-stage functionalization of drug analogues and peptides.

| S-EPMC9667918 | biostudies-literature

Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis.

Project description:Modern drug discovery relies on the continual development of synthetic methodology to address the many challenges associated with the design of new pharmaceutical agents. One such challenge arises from the enzymatic metabolism of drugs in vivo by cytochrome P450 oxidases, which use single-electron oxidative mechanisms to rapidly modify small molecules to facilitate their excretion. A commonly used synthetic strategy to protect against in vivo metabolism involves the incorporation of electron-withdrawing functionality, such as the trifluoromethyl (CF(3)) group, into drug candidates. The CF(3) group enjoys a privileged role in the realm of medicinal chemistry because its incorporation into small molecules often enhances efficacy by promoting electrostatic interactions with targets, improving cellular membrane permeability, and increasing robustness towards oxidative metabolism of the drug. Although common pharmacophores often bear CF(3) motifs in an aromatic system, access to such analogues typically requires the incorporation of the CF(3) group, or a surrogate moiety, at the start of a multi-step synthetic sequence. Here we report a mild, operationally simple strategy for the direct trifluoromethylation of unactivated arenes and heteroarenes through a radical-mediated mechanism using commercial photocatalysts and a household light bulb. We demonstrate the broad utility of this transformation through addition of CF(3) to a number of heteroaromatic and aromatic systems. The benefit to medicinal chemistry and applicability to late-stage drug development is also shown through examples of the direct trifluoromethylation of widely prescribed pharmaceutical agents.

| S-EPMC3310175 | biostudies-literature

Birch-Type Photoreduction of Arenes and Heteroarenes by Sensitized Electron Transfer.

Project description:The direct reduction of arenes and heteroarenes by visible-light irradiation remains challenging, as the energy of a single photon is not sufficient for breaking aromatic stabilization. Shown herein is that the energy accumulation of two visible-light photons allows the dearomatization of arenes and heteroarenes. Mechanistic investigations confirm that the combination of energy-transfer and electron-transfer processes generates an arene radical anion, which is subsequently trapped by hydrogen-atom transfer and finally protonated to form the dearomatized product. The photoreduction converts planar aromatic feedstock compounds into molecular skeletons that are of use in organic synthesis.

| S-EPMC6790943 | biostudies-literature

Copper-catalyzed electrophilic amination of heteroarenes and arenes by C-H zincation.

Project description:Direct amination of heteroarenes and arenes has been achieved in a one-pot C?H zincation/copper-catalyzed electrophilic amination procedure. This amination method provides an efficient and rapid approach to access a diverse range of heteroaromatic and aromatic amines including those previously inaccessible using C?H amination methods. The mild reaction conditions and good functional-group compatibility demonstrate its great potential for the synthesis of important and complex amines.

| S-EPMC4668583 | biostudies-literature