Mechanistic insights into excited-state palladium catalysis for C–S bond formations and dehydrogenative sulfonylation of amines DOI Creative Commons
Krishnamoorthy Muralirajan, Rajesh Kancherla, Bholanath Maity

et al.

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

Published: Oct. 19, 2023

Photocatalytic selective C(sp3)-H activation/cross-coupling reactions are appealing in organic synthesis. In this manuscript, we describe the development of photoexcited-state Pd-catalyzed dehydrogenative β-sulfonylation using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer C-S cross-coupling processes at room temperature. The transformation can be achieved by direct generation two distinct Pd-radical hybrid species their capability to promote different reactivities from Pd(0) chlorides, allowing for efficient conversion readily available into stable sulfonyl-substituted enamines in-depth experimental, computational, transient optical spectroscopic study catalytic applications a functionalization event provide evidence both static dynamic quenching, as well inner-sphere outer-sphere mechanisms.

Language: Английский

Electrochemical Late-Stage Functionalization DOI Creative Commons
Yulei Wang, Suman Dana, Hao Long

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

Citations

148
Ferrocene-Mediated Photocatalytic Annulation of N-Sulfonyl Ketimines on a Polycrystalline WSe2 Semiconductor Photocatalyst DOI
Yuhan Lu, Chao Wu,

Jia-Cheng Hou

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 13071 - 13076

Published: Sept. 22, 2023

A merger of heterogeneous polycrystalline WSe2 semiconductor photocatalysis and homogeneous ferrocene redox catalysis for the cascade radical coupling-annulation reactions was established. In redox-mediated photocatalysis, can improve separation photogenerated hole–electron pairs on by consuming hole via formation a cation, which triggered molecular transformations. Various benzo[e]imidazo[1,5-c][1,2,3]oxathiazine 5,5-dioxides were formed through semiheterogeneous three-component reaction N-sulfonyl ketimines, N-arylglycines, formaldehyde.

Language: Английский

Citations

121
Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator DOI
Yanwei Wang, Zhiwei Zhao, Deng Pan

et al.

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

Citations

88
Electrocarboxylation of Aryl Epoxides with CO2for the Facile and Selective Synthesis of β‐Hydroxy Acids DOI
Yanwei Wang,

Shunyao Tang,

Guoqing Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: July 30, 2022

Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides CO 2 with high chemo‐ regioselectivity under mild sustainable electrochemical conditions is described. This showed broad substrate scope good functional‐group compatibility. In addition epoxides, four‐ six‐membered cyclic ethers could all be tolerated in the reaction provide synthetically useful hydroxy acids efficiency. Further late‐stage carboxylation of complex molecules drug demonstrated its potential application pharmaceutical industry. Mechanistic studies disclosed possible pathways.

Language: Английский

Citations

78
Ferrocene/air double-mediated FeTiO3-photocatalyzed semi-heterogeneous annulation of quinoxalin-2(1H)-ones in EtOH/H2O DOI
Wen‐Tao Ouyang,

Hong‐Tao Ji,

Jun Jiang

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(94), P. 14029 - 14032

Published: Jan. 1, 2023

With both ferrocene and air as the redox catalysts, for first time, low-cost natural ilmenite (FeTiO3) was successfully used photocatalytic bond formations. Under assistance of a traceless H-bond, HCHO methylene reagent, variety imidazo[1,5-a]quinoxalinones were semi-heterogeneously photosynthesized in high yields with good functional group compatibility.

Language: Английский

Citations

54
EtOH-catalyzed electrosynthesis of imidazolidine-fused sulfamidates fromN-sulfonyl ketimines,N-arylglycines and formaldehyde DOI
Yuhan Lu,

Si‐Yu Mu,

Hongxia Li

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(14), P. 5539 - 5542

Published: Jan. 1, 2023

With formaldehyde as an atom-economical carbonyl synthon, the EtOH-catalyzed electrochemical multicomponent synthesis of various imidazolidine-fused sulfamidates under organic oxidant-free, energy-saving and mild conditions was developed.

Language: Английский

Citations

51
Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes DOI

Keming Yang,

Tian Feng, Youai Qiu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Language: Английский

Citations

49
Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp3)−H Alkenylation** DOI

Long Zou,

Xiaofan Wang,

Siqi Xiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Language: Английский

Citations

46
Single‐Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis DOI

Xin‐Yu Wang,

Yong‐Zhou Pan,

Jiarui Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 23, 2024

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single-electron transfer on electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, problems this chemistry still exist such as dosage, difficult recovery, and low efficiency. Single-atom catalysts (SACs) exhibit atom utilization excellent activity, hold great promise in addressing limitations homogeneous catalysts. In view this, we have employed Fe-SA@NC an advanced redox mediator to try change situation. was synthesized using encapsulation-pyrolysis method, it demonstrated remarkable performance a range reported reactions, construction various C-C/C-X bonds. Moreover, potential exploring new synthetic method for electrosynthesis. We develop electro-oxidative ring-opening transformation cyclopropyl amides. reaction system, showed good tolerance drug molecules with complex structures, well flow electrochemical syntheses gram-scale transformations. This work highlights SACs electrosynthesis, thereby opening avenue chemistry.

Language: Английский

Citations

30
Recent Advances in Electrocarboxylation with CO2 DOI
Siyi Wang, Tian Feng, Yanwei Wang

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(17)

Published: July 6, 2022

Abstract Carbon dioxide (CO 2 ) is an abundant, inexpensive, renewable C1 resource and the main component of greenhouse gas, thereby research for its sustainable efficient conversion has received notable attention in recent years. Electrochemical organic synthesis, as a green synthetic method, convinced to be ideal approach CO utilization. In this review, advances electrocarboxylation with were summarized through different reaction types, which would disclose great potential synthesis.

Language: Английский

Citations

70