Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Nickel Catalyzed Carbonylation/Carboxylation Sequence via Double CO₂ Incorporation.

ABSTRACT: A carbonylation-carboxylation synthetic sequence, via double CO₂ fixation, is described. The productive merger of a Ni-catalyzed cross-electrophile coupling manifold, with the use of AlCl₃, triggered a cascade reaction with the formation of three consecutive C-C bonds in a single operation. This strategy traces an unprecedented synthetic route to ketones under Lewis acid assisted carbon dioxide valorization. Computational insights revealed a unique double function of AlCl₃, and labeling (¹³CO₂) experiments validate the genuine incorporation of CO₂ in both functional groups.

SUBMITTER: Giovanelli R

PROVIDER: S-EPMC10546374 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Nickel Catalyzed Carbonylation/Carboxylation Sequence via Double CO2 Incorporation.

Giovanelli Riccardo R Lombardi Lorenzo L Pedrazzani Riccardo R Monari Magda M Reis Marta Castiñeira MC López Carlos Silva CS Bertuzzi Giulio G Bandini Marco M

Organic letters 20230905 38

A carbonylation-carboxylation synthetic sequence, via double CO2 fixation, is described. The productive merger of a Ni-catalyzed cross-electrophile coupling manifold, with the use of AlCl3, triggered a cascade reaction with the formation of three consecutive C-C bonds in a single operation. This strategy traces an unprecedented synthetic route to ketones under Lewis acid assisted carbon dioxide valorization. Computational insights revealed a unique double function of AlCl<s ...[more]

PMID: 37669466

Similar Datasets

Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO2.

Project description:Electrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C-C bonds by using electron as the clean reductant. However, activated substrates are used in most cases. Herein, we report a general and practical electro-reductive Ni-catalytic system, realizing the electrocatalytic carboxylation of unactivated aryl chlorides and alkyl bromides with CO2. A variety of unactivated aryl bromides, iodides and sulfonates can also undergo such a reaction smoothly. Notably, we also realize the catalytic electrochemical carboxylation of aryl (pseudo)halides with CO2 avoiding the use of sacrificial electrodes. Moreover, this sustainable and economic strategy with electron as the clean reductant features mild conditions, inexpensive catalyst, safe and cheap electrodes, good functional group tolerance and broad substrate scope. Mechanistic investigations indicate that the reaction might proceed via oxidative addition of aryl halides to Ni(0) complex, the reduction of aryl-Ni(II) adduct to the Ni(I) species and following carboxylation with CO2.

| S-EPMC8648755 | biostudies-literature

Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2.

Project description:The first ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2 to generate important aryl acetic acids is reported. Besides aldehyde hydrazones, a variety of ketone hydrazones, which have not been successfully applied in previous umpolung reactions with other reactive electrophiles, also show high reactivity and selectivity under mild conditions. Moreover, this operationally simple protocol features good functional group tolerance, is readily scalable, and offers easy derivation of important structures, including bioactive felbinac and adiphenine. Computational studies reveal that this umpolung reaction proceeds through the generation of a Ru-nitrenoid followed by concerted [4 + 2] cycloaddition with CO2.

| S-EPMC5982211 | biostudies-literature

Nickel-catalyzed reductive carboxylation of styrenes using CO2.

Project description:A nickel-catalyzed reductive carboxylation of styrenes using CO2 has been developed. The reaction proceeds under mild conditions using diethylzinc as the reductant. Preliminary data suggests the mechanism involves two discrete nickel-mediated catalytic cycles, the first involving a catalyzed hydrozincation of the alkene followed by a second, slower nickel-catalyzed carboxylation of the in situ formed organozinc reagent. Importantly, the catalyst system is very robust and will fixate CO2 in good yield even if exposed to only an equimolar amount introduced into the headspace above the reaction.

| S-EPMC2928647 | biostudies-literature

Electroreductive Cobalt-Catalyzed Carboxylation: Cross-Electrophile Electrocoupling with Atmospheric CO2.

Project description:The chemical use of CO2 as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carboxylations of allylic chlorides with CO2 . Styrylacetic acid derivatives were obtained with moderate to good yields and good functional group tolerance. The thus-obtained products are useful as versatile synthons of γ-arylbutyrolactones. Cyclic voltammetry and in operando kinetic analysis were performed to provide mechanistic insights into the electrocatalytic carboxylation with CO2 .

| S-EPMC7496797 | biostudies-literature

Visible-light photoredox-catalyzed umpolung carboxylation of carbonyl compounds with CO2.

Project description:Photoredox-mediated umpolung strategy provides an alternative pattern for functionalization of carbonyl compounds. However, general approaches towards carboxylation of carbonyl compounds with CO2 remain scarce. Herein, we report a strategy for visible-light photoredox-catalyzed umpolung carboxylation of diverse carbonyl compounds with CO2 by using Lewis acidic chlorosilanes as activating/protecting groups. This strategy is general and practical to generate valuable α-hydroxycarboxylic acids. It works well for challenging alkyl aryl ketones and aryl aldehydes, as well as for α-ketoamides and α-ketoesters, the latter two of which have never been successfully applied in umpolung carboxylations with CO2 (to the best of our knowledge). This reaction features high selectivity, broad substrate scope, good functional group tolerance, mild reaction conditions and facile derivations of products to bioactive compounds, including oxypheonium, mepenzolate bromide, benactyzine, and tiotropium. Moreover, the formation of carbon radicals and carbanions as well as the key role of chlorosilanes are supported by control experiments.

| S-EPMC8175691 | biostudies-literature

Pd(II)-catalyzed carboxylation of aromatic C─H bonds with CO2.

Project description:The carboxylation of nonactivated C─H bonds provides an attractive yet hitherto largely elusive chemical process to synthesize carboxylic acids by incorporation of CO2 into the chemical value chain. Here, we report on the realization of such a reaction using simple and nonactivated arenes as starting materials. A computationally designed Pd(II) complex acts as organometallic single-component catalyst, and apart from a base, necessary for thermodynamic stabilization of the intermediates, no other additives or coreagents are required. Turnover numbers up to 102 and high regioselectivities are achieved. The potential of this catalytic reaction for "green chemistry" is demonstrated by the synthesis of veratric acid, an intermediate for pharmaceutical production, from CO2 and veratrol.

| S-EPMC9897662 | biostudies-literature

Visible-Light/Nickel-Catalyzed Carboxylation of C(sp2) Bromides via Formate Activation.

Project description:A new visible-light-driven method for the carboxylation of (hetero)aryl/vinyl bromides has been developed using catalytic 4CzIPN, nickel, phenyl triflimide, and sodium formate as a carboxylation agent. Interestingly, we found catalytic phenyl triflimide plays an essential role in promoting the reaction. While many C(sp2) carboxylation reactions require harsh reagents or gaseous carbon dioxide, we demonstrate the mild and facile construction of carboxylic acids from readily available starting materials.

| S-EPMC10337029 | biostudies-literature

Palladium-catalyzed incorporation of atmospheric CO2: efficient synthesis of functionalized oxazolidinones.

Project description:Methods to incorporate atmospheric CO2 into organic molecules are on demand. Here we present two Pd-catalyzed multicomponent reactions that provide functionalized oxazolidinones from propargylamines, aryl halides and CO2 as starting materials. These transformations, devoid of high CO2 pressures, represent a streamlined stereocontrolled synthesis of previously inaccessible versions of these useful heterocycles in an atom-economic manner, as up to four new single bonds are formed in a single synthetic operation.

| S-EPMC6013789 | biostudies-literature

Synthesis of α-CF3 Amides via Palladium-Catalyzed Carbonylation of 2-Bromo-3,3,3-trifluoropropene.

Project description:Amide compounds are important organic compounds, which play an important role in biomedical chemistry, materials science, life science, and other fields. The synthesis of α-CF3 amides, especially compounds containing 3-(trifluoromethyl)-1,3,4,5-tetrahydro-2H-benzo[b][1,4]diazepine-2-one, has long been a challenge due to the tensile properties and instability of the rings. Here, we report an example of palladium-catalyzed carbonylation of CF3-containing olefin to form α-CF3 acrylamide. By controlling the ligands, we can get different amide compounds as products. This method has good substrate adaptability and functional group tolerance.

| S-EPMC9948557 | biostudies-literature

Nickel-pincer cofactor biosynthesis involves LarB-catalyzed pyridinium carboxylation and LarE-dependent sacrificial sulfur insertion.

Project description:The lactate racemase enzyme (LarA) of Lactobacillus plantarum harbors a (SCS)Ni(II) pincer complex derived from nicotinic acid. Synthesis of the enzyme-bound cofactor requires LarB, LarC, and LarE, which are widely distributed in microorganisms. The functions of the accessory proteins are unknown, but the LarB C terminus resembles aminoimidazole ribonucleotide carboxylase/mutase, LarC binds Ni and could act in Ni delivery or storage, and LarE is a putative ATP-using enzyme of the pyrophosphatase-loop superfamily. Here, we show that LarB carboxylates the pyridinium ring of nicotinic acid adenine dinucleotide (NaAD) and cleaves the phosphoanhydride bond to release AMP. The resulting biscarboxylic acid intermediate is transformed into a bisthiocarboxylic acid species by two single-turnover reactions in which sacrificial desulfurization of LarE converts its conserved Cys176 into dehydroalanine. Our results identify a previously unidentified metabolic pathway from NaAD using unprecedented carboxylase and sulfur transferase reactions to form the organic component of the (SCS)Ni(II) pincer cofactor of LarA. In species where larA is absent, this pathway could be used to generate a pincer complex in other enzymes.

| S-EPMC4878509 | biostudies-literature