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

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Dec. 6, 2021

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 used in most cases. Herein, we report a general practical electro-reductive Ni-catalytic system, realizing electrocatalytic carboxylation of unactivated aryl chlorides alkyl bromides with CO2. A variety bromides, iodides sulfonates can also undergo such reaction smoothly. Notably, realize electrochemical (pseudo)halides CO2 avoiding use sacrificial electrodes. Moreover, this economic strategy reductant features mild conditions, inexpensive catalyst, safe cheap electrodes, good functional group tolerance broad substrate scope. Mechanistic investigations indicate that might proceed via oxidative addition halides Ni(0) complex, reduction aryl-Ni(II) adduct Ni(I) species following

Language: Английский

---

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2062 - 2068

Published: Jan. 27, 2022

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated a promising synthetic method. However, dicarboxylation C─C single bonds rarely investigated. Herein we report novel electrochemical ring-opening strained rings CO2. Structurally diverse glutaric acid adipic derivatives were synthesized from substituted cyclopropanes cyclobutanes moderate high yields. In contrast oxidative ring openings, this is also first realization an electroreductive reaction rings, including commercialized ones. Control experiments suggested that radical anions carbanions might be key intermediates reaction. Moreover, process features step atom economy, mild conditions (1 atm, room temperature), good chemoselectivity functional group tolerance, low electrolyte concentration, easy derivatization products. Furthermore, conducted polymerization corresponding diesters diols obtain potential UV-shielding material self-healing function fluorine-containing polyester, whose performance tests showed applications.

Language: Английский

---

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(7), P. 2812 - 2821

Published: Feb. 9, 2021

Carboxylic acids, including amino acids (AAs), have been widely used as reagents for decarboxylative couplings. In contrast to previous couplings that release CO2 a waste byproduct, herein we report novel strategy with simultaneous utilization of both the alkyl and carboxyl components from carboxylic acids. Under this unique strategy, act bifunctional in redox-neutral carbocarboxylation alkenes. Diverse, inexpensive, readily available α-AAs take part such difunctionalizations activated alkenes via visible-light photoredox catalysis, affording variety valuable but otherwise difficult access γ-aminobutyric acid derivatives (GABAs). Additionally, series dipeptides tripeptides also participate photocatalytic carbocarboxylation. Although several challenges exist system due low concentration quantitative amount CO2, well unproductive side reactions hydrodecarboxylation hydroalkylation alkenes, excellent regioselectivity moderate high chemoselectivity are achieved. This process features catalyst loading, mild reaction conditions, step atom economy, good functional group tolerance, it is scalable. The resulting products subject efficient derivations, overall amenable applications late-stage modification complex compounds. Mechanistic studies indicate carbanion generated catalytically acts key intermediate react which situ thus remains concentration. transformation represents an sustainable organic synthesis, pharmaceutics, biochemistry.

Language: Английский

---

Nickel‐Catalyzed Asymmetric Reductive Carbo‐Carboxylation of Alkenes with CO₂

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 14068 - 14075

Published: April 1, 2021

Abstract Reductive carboxylation of organo (pseudo)halides with CO 2 is a powerful method to provide carboxylic acids quickly. Notably, the catalytic reductive carbo‐carboxylation unsaturated hydrocarbons via fixation highly challenging but desirable approach for structurally diverse acids. There are only few reports and no examples alkenes transition metal catalysis. We report first asymmetric nickel A variety aryl (pseudo)halides, such as bromides, triflates inert chlorides particular note, undergo reaction smoothly give important oxindole‐3‐acetic acid derivatives bearing C3‐quaternary stereocenter. This transformation features mild conditions, wide substrate scope, facile scalability, good excellent chemo‐, regio‐ enantioselectivities. The highlights formal synthesis (−)‐Esermethole, (−)‐Physostigmine (−)‐Physovenine, total (−)‐Debromoflustramide B, (−)‐Debromoflustramine B (+)‐Coixspirolactam A; thereby, opening an avenue chiral natural products .

Language: Английский

---

From Hydrogenation to Transfer Hydrogenation to Hydrogen Auto-Transfer in Enantioselective Metal-Catalyzed Carbonyl Reductive Coupling: Past, Present, and Future

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(9), P. 5572 - 5585

Published: April 22, 2021

Atom-efficient processes that occur via addition, redistribution or removal of hydrogen underlie many large volume industrial and pervade all segments chemical industry. Although carbonyl addition is one the oldest most broadly utilized methods for C-C bond formation, delivery non-stabilized carbanions to compounds has relied on premetalated reagents metallic/organometallic reductants, which pose issues safety challenges vis-à-vis implementation. Catalytic reductive couplings promoted hydrogenation, transfer hydrogenation auto-transfer allow abundant unsaturated hydrocarbons serve as substitutes organometallic reagents, enabling formation in absence stoichiometric metals. This perspective (a) highlights past milestones catalytic auto-transfer, (b) summarizes current enantioselective couplings, (c) describes future opportunities based patterns reactivity animate transformations this type.

Language: Английский

---

Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 26, 2022

Herein, an electroreductive carboxylation of organic carbon-halogen bonds (X=Br and Cl) promoted by catalytic amounts naphthalene as mediator is reported. This transformation proceeds smoothly under mild conditions with a broad substrate scope 59 examples, affording the valuable versatile carboxylic acids in moderate to excellent yields without need costly transition metal, wasted stoichiometric metal reductants, or sacrificial anodes. Further late-stage carboxylations natural product drug derivatives demonstrate its synthetic utility. Mechanistic studies confirmed activation via single-electron transfer key role this reaction.

Language: Английский

---

Challenges and recent advancements in the transformation of CO₂into carboxylic acids: straightforward assembly with homogeneous 3d metals

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(22), P. 9371 - 9423

Published: Jan. 1, 2022

The transformation of carbon dioxide (CO2) into useful chemicals, advanced materials, and energy is a long-standing challenge in both fundamental science industry. In recent years, utilization CO2 the presence inexpensive non-negligible environmentally friendly 3d metal-based catalysts (Fe, Mn, Co, Ni, Cu Ti) has become one most attractive topics. Particular attention been given to synthesis carboxylic acids their derivatives since these molecules serve as key intermediates chemical, fertilizer, pharmaceutical sectors. Considering numerous challenges linked with reactivity, number research groups have recently focused on by following thermo-, photo-, electrochemical strategies. However, facile access such remains vital catalysis organic owing high stability molecule which atom highest oxidation state. Another hurdle solve selectivity issue caused reaction different catalytic systems reactive functional group-containing molecules. Despite all issues, wide range transition applied this direction, but cheaper price inherent metals are at forefront domain. these, we aim summarise advances (over past five years) 3d-metal complexes reactivity towards activation for acids. Furthermore, discuss current trends, knowledge gaps, invigorating perspectives future advances.

Language: Английский

---

Nanoporous {Y₂}-Organic Frameworks for Excellent Catalytic Performance on the Cycloaddition Reaction of Epoxides with CO₂ and Deacetalization–Knoevenagel Condensation

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(16), P. 18589 - 18599

Published: April 13, 2022

Stable metal-organic frameworks containing periodically arranged nanosized pores and active Lewis acid-base sites are considered as ideal candidates for efficient heterogeneous catalysis. Herein, the exquisite combination of [Y2(CO2)7(H2O)2] cluster (abbreviated {Y2}) multifunctional linker 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (H6TDP) led to a nanoporous framework {[Y2(TDP)(H2O)2]·5H2O·4DMF}n (NUC-53, NUC = North University China), which is rarely reported binuclear three-dimensional (3D) with hierarchical tetragonal-microporous (0.78 nm) octagonal-nanoporous (1.75 channels. The inner walls these channels aligned by {Y2} clusters plentifully coexisted YIII ions Npyridine atoms. Furthermore, NUC-53 has quite large void volume ∼65.2%, significantly higher than most documented 3D rare-earth-based MOFs. performed catalytic experiments exhibited that activated showed high activity on cycloaddition reactions CO2 styrene oxide under mild conditions excellent turnover number (TON: 1980) frequency (TOF: 495 h-1). Moreover, deacetalization-Knoevenagel condensation benzaldehyde dimethyl acetal malononitrile could be efficiently prompted catalyst NUC-53. These findings not only pave way construction MOF based rare-earth variety activities but also provide some new insights into mechanism.

Language: Английский

---

Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO₂ via Photoredox Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8551 - 8559

Published: April 4, 2022

A new strategy for the direct cleavage of C(sp3)-OH bond has been developed via activation free alcohols with neutral diphenyl boryl radical generated from sodium tetraphenylborate under mild visible light photoredox conditions. This verified by cross-electrophile coupling and carbon dioxide synthesis carboxylic acids. Direct transformation a range primary, secondary, tertiary benzyl to acids achieved. Control experiments computational studies indicate that undergoes homolysis bond, generating alkyl radicals. After reducing into anion conditions, following carboxylation CO2 affords product.

Language: Английский

---

Dicarboxylation of Alkenes with CO₂ and Formate via Photoredox Catalysis

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 2149 - 2155

Published: Jan. 25, 2023

Herein, a photocatalytic strategy for the synthesis of succinic acids by alkene dicarboxylation with carbon dioxide (CO2) and formate salt as synergistic sources is described. The acts both C1 source reductant in reaction catalytic amount 1,4-diazabicyclo[2.2.2]octane (DABCO) hydrogen atom transfer reagent. Various mono-, di-, trisubstituted alkenes, acrylate, acrylamide, indole derivatives could be converted to corresponding diacids, which provided potential useful applications medicinal chemistry polymer industry.

Language: Английский

---