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

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Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO₂

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 3, 2023

Carboxylation of easily available alkenes with CO2 is highly important to afford value-added carboxylic acids. Although dicarboxylation activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging unactivated 1,n-dienes (n>3) remains unexplored. Herein, we report first skipped dienes via electrochemistry, affording valuable dicarboxylic Control experiments and DFT calculations support single electron transfer (SET) reduction its radical anion, which followed by sluggish addition SET unstabilized alkyl radicals carbanions nucleophilic attack on give desired products. This reaction features mild conditions, broad substrate scope, facile derivations products promising application in polymer chemistry.

Language: Английский

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Catalytic Regio- and Enantioselective Boracarboxylation of Arylalkenes with CO₂ and Diboron

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2888 - 2894

Published: Jan. 26, 2024

Catalytic asymmetric carboxylation of readily available alkenes with CO2, an abundant and sustainable one-carbon building block, that gives access to value-added α-stereogenic carboxylic acids in atom- step-economic manner is highly attractive. However, it has remained a formidable challenge for the synthetic community. Here, first example Cu-catalyzed regio- enantioselective boracarboxylation reaction on various arylalkenes diboron under atmospheric pressure CO2 described, which afforded variety chiral β-boron-functionalized α-aryl up 87% yield 97% ee mild conditions. Importantly, α-substituted could also be subject this protocol excellent enantiopurities, thereby rendering efficient approach generation enantioenriched α-chiral all-carbon quaternary center. Moreover, high functional group tolerance, scalable synthesis, facile bioactive compounds, like (−)-scopolamine, (−)-anisodamine, (−)-tropicamide, further demonstrated utility strategy.

Language: Английский

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Kinetically-Controlled Ni-Catalyzed Direct Carboxylation of Unactivated Secondary Alkyl Bromides without Chain Walking

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1753 - 1759

Published: Jan. 9, 2024

Herein, we report the direct carboxylation of unactivated secondary alkyl bromides enabled by merger photoredox and nickel catalysis, a previously inaccessible endeavor in arena. Site-selectivity is dictated kinetically controlled insertion CO2 at initial C(sp3)–Br site rapid formation Ni(I)–alkyl species, thus avoiding undesired β-hydride elimination chain-walking processes. Preliminary mechanistic experiments reveal subtleties stereoelectronic effects for guiding reactivity site-selectivity.

Language: Английский

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Direct C–C Bond Formation of Allylic Alcohols with CO₂ toward Carboxylic Acids by Photoredox/Nickel Dual Catalysis

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(5), P. 2781 - 2787

Published: Feb. 11, 2022

Carboxylation of allylic alcohols with carbon dioxide is accomplished by photoredox/nickel dual catalysis, generating linear acids exclusively good Z/E stereoselectivity. Hantzsch ester employed as the reductant instead stoichiometric metallic reductants, and reaction can be conducted under room temperature a blue LED light source. Mechanistic studies reveal that presence water in this catalytic system critical to success reaction, more likely proceed oxidative addition situ formed hydrogen carbonate.

Language: Английский

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Translating Planar Heterocycles into Three‐Dimensional Analogs by Photoinduced Hydrocarboxylation**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 18, 2023

The rapid preparation of complex three-dimensional (3D) heterocyclic scaffolds is a key challenge in modern medicinal chemistry. Despite the increased probability clinical success for small molecule therapeutic candidates with 3D complexity, new drug targets remain dominated by flat molecules due to abundance coupling reactions available their construction. In principle, heteroarene hydrofunctionalization offer an opportunity transform readily accessible planar into more three-dimensionally analogs through introduction single molecular vector. Unfortunately, dearomative limited. Herein, we report strategy enable hydrocarboxylation indoles and related heterocycles. This reaction represents rare example that meets numerous requirements broad implementation discovery. transformation highly chemoselective, scope, operationally simple, amenable high-throughput experimentation (HTE). Accordingly, this process will allow existing libraries heteroaromatic compounds be translated diverse exploration classes medicinally relevant molecules.

Language: Английский

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Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

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Straightforward synthesis of functionalized γ-Lactams using impure CO2 stream as the carbon source

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 22, 2023

Abstract Direct utilization of CO 2 into organic synthesis finds enormous applications to synthesize pharmaceuticals and fine chemicals. However, pure gas is essential achieve these transformations, the purification highly cost energy intensive. Considering this, we describe a straightforward synthetic route for γ-lactams, pivotal core structure bioactive molecules, by using commercially available starting materials (alkenes amines) impure stream (exhaust collected from car) as carbon source. This blueprint features broad scope, excellent functional group compatibility application late-stage transformation existing natural products functionalized γ-lactams. We believe that our strategy will provide direct access γ-lactams in very sustainable way also enhance Carbon Capture Utilization (CCU) strategy.

Language: Английский

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Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO₂

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 26, 2024

Abstract Upgrading CO 2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the of centrally carboxylic acids has been achieved, construction axially with never reported date. Herein, we report first synthesis , which enabled by nickel‐catalyzed dynamic kinetic reductive carboxylation racemic aza‐biaryl triflates. A variety acids, are valuable but difficult obtain catalysis, generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents using stoichiometric materials. Mechanistic investigations indicate process induced nickel catalysis.

Language: Английский

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Visible-light-driven alkene dicarboxylation with formate and CO₂ under mild conditions

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 6178 - 6183

Published: Jan. 1, 2024

Low-cost formate salt was used as the reductant and part of carboxyl source in a visible-light-driven dicarboxylation diverse alkenes, including simple styrenes. The highly competing hydrocarboxylation side reaction successfully overridden. Good yields products were obtained under mild conditions at ambient temperature pressure CO

Language: Английский

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