Decarboxylative Triazolation Enables Direct Construction of Triazoles from Carboxylic Acids DOI Creative Commons
Hang T. Dang, Viet D. Nguyen, Graham C. Haug

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 3(3), P. 813 - 822

Published: Feb. 16, 2023

Triazoles have major roles in chemistry, medicine, and materials science, as centrally important heterocyclic motifs bioisosteric replacements for amides, carboxylic acids, other carbonyl groups, well some of the most widely used linkers click chemistry. Yet, chemical space molecular diversity triazoles remains limited by accessibility synthetically challenging organoazides, thereby requiring preinstallation azide precursors restricting triazole applications. We report herein a photocatalytic, tricomponent decarboxylative triazolation reaction that first time enables direct conversion acids to single-step, triple catalytic coupling with alkynes simple reagent. Data-guided inquiry accessible indicates transformation can improve access structural complexity triazoles. Experimental studies demonstrate broad scope synthetic method includes variety acid, polymer, peptide substrates. When performed absence alkynes, also be obviating preactivation specialized reagents providing two-pronged approach C–N bond-forming functional group interconversions.

Language: Английский

Ligand‐to‐Metal Charge Transfer (LMCT) Photochemistry at 3d‐Metal Complexes: An Emerging Tool for Sustainable Organic Synthesis DOI Creative Commons
Fabio Juliá

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(19)

Published: Aug. 11, 2022

Abstract Despite the rich photochemistry of 3d‐metal complexes, utilization excited‐state reactivity these compounds in organic synthesis has been historically overlooked. The advent photoredox catalysis changed perception synthetic chemists towards photochemistry, and nowadays potential photoinduced, outer‐sphere single‐electron transfer events is widely recognized. More recently, an emerging new mode photoactivation taken spotlight, based on inner‐sphere triggered by population ligand‐to‐metal charge‐transfer (LMCT) excited states. Contrarily to photoredox, LMCT‐activation does not rely matching redox potentials, offers unique profiles particularly well suited Earth‐abundant metal complexes. Those appealing features are propelling development methods using this blueprint generate highly reactive open‐shell species under mild conditions. aim contribution provide a didactical tool for comprehension concept facilitate methodologies achieve sustainable chemical transformations.

Language: Английский

Citations

230
Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation DOI
Xiao‐Li Lai, Ming Chen, Yuqi Wang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20201 - 20206

Published: Oct. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Language: Английский

Citations

99
Recent Advances in Reactions Involving Carbon Dioxide Radical Anion DOI
Wei Xiao, Jun Zhang, Jie Wu

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 15991 - 16011

Published: Nov. 28, 2023

Carbon dioxide radical anion (CO2•–) is a highly reactive nucleophilic species that has recently emerged in organic chemistry as strong single electron donor (reductant) and reactant for the synthesis of carboxylic acids. In general, CO2•– can be generated by either direct reduction CO2 or HAT formate salts. Achievements reactions involving have been witnessed recent years. This Review summarizes advances highlighting some challenges identifying potential areas improvement, which may offer inspiration future studies.

Language: Английский

Citations

56
Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization DOI
Liubo Li, Yan Yao, Niankai Fu

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

Citations

55
Continuous Flow Decarboxylative Monofluoroalkylation Enabled by Photoredox Catalysis DOI Creative Commons

F Pasca,

Yuri Gelato,

Michael Andresini

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 684 - 692

Published: Feb. 2, 2025

Herein, we report a scalable and mild strategy for the monofluoroalkylation of wide array Giese acceptors via visible-light-mediated photoredox catalysis in continuous flow. The use flow technology significantly enhances productivity scalability, whereas mildness conditions functional group tolerance are ensured by leveraging 4CzIPN, transition-metal-free organic photocatalyst. Structurally diverse secondary tertiary monofluoroalkyl radicals can thus be accessed from readily available α-monofluorocarboxylic acids. Given reaction conditions, this protocol is also amenable to late-stage functionalization biologically relevant molecules such as menthol, amantadine, bepotastine, estrone derivatives, rendering it suitable application drug discovery programs, which introduction fluorinated fragments highly sought after. This method was extended enable reductive multicomponent radical-polar crossover transformation rapidly increase complexity assembled architectures single synthetic operation.

Language: Английский

Citations

3
Mechanistic Insight into the Photoinduced Decarboxylative Radical Addition of Carboxylic Acid to Alkenes in a Two-Molecule Photoredox System DOI

Toshiki Furutani,

Yasunori Matsui,

Ryoga Hashimoto

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

The detailed mechanism of photoinduced decarboxylative radical addition to alkenes using both the effect an electron donor (ED)/electron acceptor (EA) and laser flash photolysis in a two-molecule photoredox system was investigated. concentration EA•- played important role photoreaction could be controlled by varying concentrations ED/EA their identity, which influenced ΔGPET. Higher larger negative ΔGPET led higher EA•-, thereby increasing yield adduct; however, large for generation EDA complex hindered decarboxylation. is simple can easily tuned adjusting type (ΔGPET) through replacement ED/EA, easier than modulating oxidation/reduction potential one-molecule systems.

Language: Английский

Citations

2
Alcohols as Alkylating Agents: Photoredox‐Catalyzed Conjugate Alkylation via In Situ Deoxygenation DOI
Johnny Wang, Holt A. Sakai, David W. C. MacMillan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(35)

Published: June 21, 2022

The rapid exploration of sp

Language: Английский

Citations

50
Electrophotochemical Decarboxylative Azidation of Aliphatic Carboxylic Acids DOI
Yukang Wang, Liubo Li, Niankai Fu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10661 - 10667

Published: Aug. 16, 2022

We report an electrophotochemical metal-catalyzed strategy that harnesses the power of light and electricity for radical decarboxylative functionalization aliphatic carboxylic acids. This environmentally friendly protocol smoothly converts a diverse array acids into corresponding alkyl azides without using chemical oxidants or azido-group transfer reagents. The visible energy electric can be applied in spatially separated fashion with modular electro-flow-cell large-scale synthesis.

Language: Английский

Citations

50
Photocatalytic coupling of electron-deficient alkenes using oxalic acid as a traceless linchpin DOI Creative Commons
Zugen Wu, Mingyue Wu, Kun Zhu

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(4), P. 978 - 988

Published: Jan. 16, 2023

Language: Английский

Citations

31
Decarboxylative, Radical C–C Bond Formation with Alkyl or Aryl Carboxylic Acids: Recent Advances DOI Creative Commons
Joshua D. Tibbetts, Alexander J. Cresswell,

Hannah E. Askey

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(20), P. 3239 - 3250

Published: April 26, 2023

Abstract The ubiquity of carboxylic acids as naturally derived or man-made chemical feedstocks has spurred the development powerful, decarboxylative C–C bond-forming transformations for organic synthesis. Carboxylic benefit not only from extensive commercial availability, but are stable surrogates organohalides organometallic reagents in transition-metal-catalysed cross-coupling. Open shell reactivity (or derivatives thereof) to furnish carbon-centred radicals is proving transformative synthetic chemistry, enabling novel and strategy-level C(sp3)–C bond disconnections with exquisite chemoselectivity. This short review will summarise several latest advances this ever-expanding area. 1 Introduction 2 Improved Decarboxylative Arylations 3 sp3–sp3 Cross-Coupling Acids Aliphatic Bromides 4 Alcohols Amines 5 Doubly 6 Bond Formation (Hetero)aryl 7 Conclusions

Language: Английский

Citations

27