Bidirectional Elongation Strategy Using Ambiphilic Radical Linchpin for Modular Access to 1,4-Dicarbonyls via Sequential Photocatalysis DOI
Akira Matsumoto, Natsumi Maeda, Keiji Maruoka

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20344 - 20354

Published: July 25, 2023

Organic molecules that can be connected to multiple substrates by sequential C-C bond formations utilized as linchpins in multicomponent processes. While they are useful for rapidly increasing molecular complexity, most of the reported linchpin coupling methods rely on use organometallic species strong carbon nucleophiles form bonds, which narrows functional group compatibility. Here, we describe a metal-free, radical-mediated approach using formyl-stabilized phosphonium ylide multifunctional under visible-light photoredox conditions. The present method uses ambiphilic character ylide, serves both nucleophilic and an electrophilic carbon-centered radical source. stepwise controllable generation these intermediates allows photocatalysis involving two mechanistically distinct additions, initiated same photocatalyst one pot with high tolerance. methodology enables bidirectional assembly electronically differentiated alkene fragments thus offers rapid modular access 1,4-dicarbonyl compounds versatile synthetic intermediates.

Language: Английский

Dicarboxylation of Alkenes with CO2 and Formate via Photoredox Catalysis DOI
Pei Xu, Sai Wang, Hui Xu

et al.

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

Citations

62
Radical Hydrocarboxylation of Unactivated Alkenes via Photocatalytic Formate Activation DOI
Sara N. Alektiar, Jimin Han, Yun Dang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10991 - 10997

Published: May 15, 2023

Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation formate salts. We illustrate that an alternative initiation mechanism circumvents limitations prior approaches and enables this challenging substrate class. Specifically, found accessing requisite thiyl radical initiator without exogenous chromophore eliminates major byproducts have plagued attempts exploit similar reactivity for alkene substrates. This redox-neutral method is technically simple execute effective across broad range Feedstock alkenes, such as ethylene, are hydrocarboxylated at ambient temperature pressure. A series cyclization experiments indicate how described in report can be diverted by more complex processes.

Language: Английский

Citations

62
Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO2 DOI
Wei Zhang, Li‐Li Liao, Li Li

et al.

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

Citations

59
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

55
Metallaphotoredox-enabled aminocarboxylation of alkenes with CO2 DOI
Jun‐Ping Yue,

Jincheng Xu,

Hai‐Tian Luo

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(10), P. 959 - 968

Published: Sept. 21, 2023

Language: Английский

Citations

53
Photoredox/HAT-Catalyzed Dearomative Nucleophilic Addition of the CO2 Radical Anion to (Hetero)Aromatics DOI
Saeesh R. Mangaonkar, Hiroki Hayashi, Hideaki Takano

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2482 - 2488

Published: Feb. 3, 2023

The radical anion of CO2 (CO2•–) is a strongly nucleophilic species with rapidly emerging applications in contemporary organic chemistry. This exhibits high reactivity single-electron reduction reactions due to the concomitant release stable CO2, or Giese-type reactions, especially for electron-deficient alkenes and styrene derivatives. In contrast previous reports, we herein disclose development robust method introduction CO2•–, which can be generated from cesium formate under photoredox/hydrogen atom transfer (HAT) catalysis, into heteroaromatics such as benzofuran, benzothiophene, indole derivatives afford synthetically useful α-oxy, α-thio, α-amino acid moderate yield. addition, when using naphthalene derivatives, both addition occur simultaneously produce carboxylated tetrahydronaphthalene good Moreover, one tetrahydronaphthalenes that bear cyano group was transformed corresponding γ-butyrolactam via functionality through hydrogenation followed by cyclization. To best our knowledge, these dearomative carboxylation metal formates photoredox/HAT conditions are unprecedented, thus providing synthetic option C1 source (hetero)aromatics.

Language: Английский

Citations

50
Switchable divergent di- or tricarboxylation of allylic alcohols with CO2 DOI
Bo Yu, Yi Liu,

Han-Zhi Xiao

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(3), P. 938 - 951

Published: Jan. 10, 2024

Language: Английский

Citations

25
Photoredox-Catalyzed Defluorinative Carboxylation of gem-Difluorostyrenes with Formate Salt DOI
Chao Sun, Quan Zhou, Chuan‐Ying Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 883 - 888

Published: Jan. 22, 2024

Herein, we present a transition-metal-free, easy handling protocol for regioselective carboxylation of gem-difluorostyrenes with sodium formate as the C1 source. 30 examples α-fluoracrylates were obtained in yields to 80% under these conditions. A defluorinative monofluorovinyl intermediate and consecutive photoinduced electron transfer mechanism proposed after investigation.

Language: Английский

Citations

25
Characterization of A π–π stacking cocrystal of 4-nitrophthalonitrile directed toward application in photocatalysis DOI Creative Commons
Ting Xue, Cheng Ma, Le Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 16, 2024

Abstract Photoexcitation of the electron-donor-acceptor complexes have been an effective approach to achieve radicals by triggering electron transfer. However, catalytic version complex photoactivation is quite underdeveloped comparing well-established utilization electronically biased partners. In this work, we utilize 4-nitrophthalonitrile as acceptor facilitate efficient π-stacking with electron-rich aromatics form complex. The characterization and energy profiles on cocrystal 1,3,5-trimethoxybenzene disclose that transfer highly favorable under light irradiation. This catalyst can be efficiently applied in benzylic C−H bond developing Giese reaction alkylanisoles oxidation benzyl alcohols. A broad scope tolerated a mechanism also proposed. Moreover, corresponding π-anion interaction potassium formate further hydrocarboxylation alkenes efficiently.

Language: Английский

Citations

17
Photocatalytic 1,3-dicarboxylation of unactivated alkenes with CO2 DOI

Han-Zhi Xiao,

Bo Yu,

Si‐Shun Yan

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 50, P. 222 - 228

Published: July 1, 2023

Language: Английский

Citations

35