α‐Amino Acids: An Emerging Versatile Synthon in Visible Light‐Driven Decarboxylative Transformations DOI
Tianju Shao,

Xu Ban,

Zhiyong Jiang

и другие.

The Chemical Record, Год журнала: 2023, Номер 23(10)

Опубликована: Июнь 5, 2023

Abstract α‐Amino acids have been widely recognized as environmental‐benign and non‐fossil carbon sources both in biological synthetic chemistry. In recent years, with the remarkable development of visible‐light photocatalysis organic synthesis, α‐amino acid its derivatives received tremendous attention radical precursors via photocatalyzed decarboxylation, thus realizing diverse aminoalkylated transformations or constructions novel N ‐bearing heterocyclic motifs by taking advantage ‐atoms from acid. This review aims to provide a comprehensive update on exploitation visible light photocatalysis, particular emphasis types employed their distinct mechanisms applied wherein.

Язык: 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, Год журнала: 2022, Номер 14(19)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

232
Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation DOI
Xiao‐Li Lai, Ming Chen, Yuqi Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(44), С. 20201 - 20206

Опубликована: Окт. 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.

Язык: Английский

Процитировано

100
Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization DOI
Liubo Li, Yan Yao, Niankai Fu

и другие.

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(21)

Опубликована: Апрель 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.

Язык: Английский

Процитировано

58
Recent Advances in Reactions Involving Carbon Dioxide Radical Anion DOI
Wei Xiao, Jun Zhang, Jie Wu

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 15991 - 16011

Опубликована: Ноя. 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.

Язык: Английский

Процитировано

58
Continuous Flow Decarboxylative Monofluoroalkylation Enabled by Photoredox Catalysis DOI Creative Commons

F Pasca,

Yuri Gelato,

Michael Andresini

и другие.

JACS Au, Год журнала: 2025, Номер 5(2), С. 684 - 692

Опубликована: Фев. 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.

Язык: Английский

Процитировано

4
Alcohols as Alkylating Agents: Photoredox‐Catalyzed Conjugate Alkylation via In Situ Deoxygenation DOI
Johnny Wang, Holt A. Sakai, David W. C. MacMillan

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(35)

Опубликована: Июнь 21, 2022

The rapid exploration of sp

Язык: Английский

Процитировано

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

и другие.

ACS Catalysis, Год журнала: 2022, Номер 12(17), С. 10661 - 10667

Опубликована: Авг. 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.

Язык: Английский

Процитировано

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

и другие.

Chem, Год журнала: 2023, Номер 9(4), С. 978 - 988

Опубликована: Янв. 16, 2023

Язык: Английский

Процитировано

32
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

и другие.

Synthesis, Год журнала: 2023, Номер 55(20), С. 3239 - 3250

Опубликована: Апрель 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

Язык: Английский

Процитировано

28
Visible Light Photoredox-Catalyzed Decarboxylative Alkylation of 3-Aryl-Oxetanes and Azetidines via Benzylic Tertiary Radicals and Implications of Benzylic Radical Stability DOI Creative Commons
Maryne A. J. Dubois, Juan J. Rojas, Alistair J. Sterling

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(10), С. 6476 - 6488

Опубликована: Март 3, 2023

Four-membered heterocycles offer exciting potential as small polar motifs in medicinal chemistry but require further methods for incorporation. Photoredox catalysis is a powerful method the mild generation of alkyl radicals C–C bond formation. The effect ring strain on radical reactivity not well understood, with no studies that address this question systematically. Examples reactions involve benzylic are rare, and their challenging to harness. This work develops functionalization oxetanes azetidines using visible light photoredox prepare 3-aryl-3-alkyl substituted derivatives assesses influence heterosubstitution small-ring radicals. 3-Aryl-3-carboxylic acid suitable precursors tertiary oxetane/azetidine which undergo conjugate addition into activated alkenes. We compare oxetane other systems. Computational indicate Giese additions unstrained acrylates reversible result low yields dimerization. Benzylic part strained ring, however, less stable more π-delocalized, decreasing dimer increasing product Oxetanes show high due Bent's rule rendering irreversible.

Язык: Английский

Процитировано

26