Cobalt-catalyzed enantioselective C–H/N–H annulation of aryl sulfonamides with allenes or alkynes: facile access to C–N axially chiral sultams DOI Creative Commons

Xiao‐Ju Si,

Xiaofang Zhao, Jianli Wang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(26), P. 7291 - 7303

Published: Jan. 1, 2023

Herein we report a cobalt-catalyzed enantioselective C-H/N-H annulation of aryl sulfonamides with allenes and alkynes, using either chemical or electrochemical oxidation. By O2 as the oxidant, proceeds efficiently low catalyst/ligand loading 5 mol% tolerates wide range allenes, including 2,3-butadienoate, allenylphosphonate, phenylallene, resulting in C-N axially chiral sultams high enantio-, regio-, position selectivities. The alkynes also exhibits excellent enantiocontrol (up to >99% ee) variety functional sulfonamides, internal terminal alkynes. Furthermore, oxidative is achieved simple undivided cell, demonstrating versatility robustness cobalt/Salox system. gram-scale synthesis asymmetric catalysis further highlight practical utility this method.

Language: Английский

Electrochemical hydrogenation and oxidation of organic species involving water DOI
Cuibo Liu, Fanpeng Chen, Bo‐Hang Zhao

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(4), P. 277 - 293

Published: March 25, 2024

Language: Английский

Citations

68
A tutorial on asymmetric electrocatalysis DOI
Jonas Rein, Samson B. Zacate, Kaining Mao

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(23), P. 8106 - 8125

Published: Jan. 1, 2023

This tutorial review delves into the unique advantages of electrochemistry in context asymmetric catalysis, first providing a brief introduction to electrosynthesis, then exploring representative case studies with mechanistic focus.

Language: Английский

Citations

65
Constructing CoO/Mo2C Heterostructures with Interfacial Electron Redistribution Induced by Work Functions for Boosting Overall Water Splitting DOI Open Access
Hanyang Chen, Lei Yang,

Rongxu Wang

et al.

Small, Journal Year: 2023, Volume and Issue: 19(49)

Published: Aug. 23, 2023

Space charge transfer of heterostructures driven by the work-function-induced built-in field can regulate electronic structure catalysts and boost catalytic activity. Herein, an epitaxial heterojunction catalyst CoO/Mo2 C with interfacial electron redistribution induced work functions (WFs) is constructed for overall water splitting via a novel top-down strategy. Theoretical simulations experimental results unveil that WFs-induced facilitates from CoO to Mo2 through formed "Co─C─Mo" bond at interface C, achieving redistribution, further optimizing Gibbs free energy primitive reaction step then accelerating kinetics hydrogen evolution (HER). As expected, effects exhibits excellent HER activity only needing overpotential 107 mV achieve 10 mA cm-2 stability 60-h continuous catalyzing. Besides, assembled behaves outstanding performance toward (1.58 V ). This provides possibility designing materials based on arising application in other fields.

Language: Английский

Citations

63
Atomically dispersed Cu coordinated Rh metallene arrays for simultaneously electrochemical aniline synthesis and biomass upgrading DOI Creative Commons

Qiqi Mao,

Mu Xu,

Wenxin Wang

et al.

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

Published: Sept. 14, 2023

Organic electrocatalytic conversion is an essential pathway for the green of low-cost organic compounds to high-value chemicals, which urgently demands development efficient electrocatalysts. Here, we report a Cu single-atom dispersed Rh metallene arrays on foam cathodic nitrobenzene electroreduction reaction and anodic methanol oxidation reaction. In coupled system, Cusingle-atom-Rh requires only low voltages 1.18 V reach current densities 100 mA cm-2 generating aniline formate, with up ~100% conversion/ selectivity over ~90% formate Faraday efficiency, achieving synthesis chemicals. Density functional theory calculations reveal electron effect between host catalytic mechanism. The synergistic H*-spillover can improve process reduce energy barrier process, thus enhancing activity target product selectivity.

Language: Английский

Citations

62
Cobalt-catalyzed atroposelective C−H activation/annulation to access N−N axially chiral frameworks DOI Creative Commons
Tong Li, Linlin Shi,

Xinhai Wang

et al.

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

Published: Aug. 29, 2023

The N-N atropisomer, as an important and intriguing chiral system, was widely present in natural products, pharmaceutical lead compounds, advanced material skeletons. anisotropic structural characteristics caused by its special axial rotation have always been one of the challenges that chemists strive to overcome. Herein, we report efficient method for enantioselective synthesis axially frameworks via a cobalt-catalyzed atroposelective C-H activation/annulation process. reaction proceeds under mild conditions using Co(OAc)2·4H2O catalyst with salicyl-oxazoline (Salox) ligand O2 oxidant, affording variety products high yields enantioselectivities. This protocol provides approach facile construction atropisomers further expands range derivatives. Additionally, electrocatalysis, desired were also successfully achieved good excellent efficiencies

Language: Английский

Citations

53
Electrocatalytic Synthesis of Pyridine Oximes using in Situ Generated NH2OH from NO species on Nanofiber Membranes Derived from NH2‐MIL‐53(Al) DOI

Runan Xiang,

Shihan Wang, Peisen Liao

et al.

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

Published: Sept. 20, 2023

Pyridine oximes produced from aldehyde or ketone with hydroxylamine (NH2 OH) have been widely applied in pharmaceutics, enzymatic and sterilization. However, the important raw material NH2 OH exhibits corrosive unstable properties, leading to substantial energy consumption during storage transportation. Herein, this work presents a novel method for directly synthesizing highly valuable pyridine using situ generated electrocatalytic NO reduction well-design nanofiber membranes (Al-NFM) derived -MIL-53(Al). Particularly, 2-pyridinealdoxime, precursor of antidote pralidoxime (2-PAM) nerve agents suffering scarcity high cost, was achieved Faraday efficiency up 49.8 % yield 92.1 %, attributing selectivity production on Al-NFM, further easily reacted iodomethane produce 2-PAM. This study proposes creative approach, having wide universality other range functional groups, which not only facilitates conversion exhaust gas (NO) waste water (NO2- ) into chemicals especially utilization through electrochemistry, but also holds significant potential synthesis neuro detoxifying drugs humanity security.

Language: Английский

Citations

52
Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp3)–C(sp3) Cross Coupling DOI
Yang Gao,

Benxiang Zhang,

Jiayan He

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11518 - 11523

Published: May 16, 2023

The first examples of enantioselective doubly decarboxylative cross coupling are disclosed. Malonate half amides smoothly coupled to a variety primary carboxylic acids after formation the corresponding redox-active esters under Ni-electrocatalytic conditions using new chiral ligand based on PyBox, resulting in with α-alkylated stereocenters. scope reaction is broad, tolerating numerous functional groups, and uniformly proceeds high ee. Finally, potential utility this radical–radical reductive simplify synthesis demonstrated case studies.

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

48
Room Temperature Construction of Vicinal Amino Alcohols via Electroreductive Cross-Coupling of N-Heteroarenes and Carbonyls DOI

Maorui Wang,

Chengqian Zhang, Chenggang Ci

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10967 - 10973

Published: April 19, 2023

Despite the widespread applications of α-hydroxyalkyl cyclic amines, direct and diverse access to such a class unique vicinal amino alcohols still remains, date, challenge. Here, through strategy electroreductive α-hydroxyalkylation inactive N-heteroarenes with ketones or electron-rich arylaldehydes, we describe room temperature approach for construction which features broad substrate scope, operational simplicity, high chemoselectivity, no need pressurized H2 gas transition metal catalysts. The zinc ion generated from anode oxidation plays crucial role in activation both reactants by decreasing their reduction potentials. electroreduction combination Lewis acids this work is anticipated develop more useful transformations.

Language: Английский

Citations

47
Contact-electro-catalysis (CEC) DOI
Ziming Wang, Xuanli Dong, Wei Tang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4349 - 4373

Published: Jan. 1, 2024

Contact-electro-catalysis (CEC) is an emerging field that utilizes electron transfer occurring at the liquid–solid and even liquid–liquid interfaces because of contact-electrification effect to stimulate redox reactions.

Language: Английский

Citations

44