Metallaphotoredox deuteroalkylation utilizing thianthrenium salts DOI Creative Commons

Mengjie Jiao,

Jie Zhang, Minyan Wang

et al.

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

Published: June 13, 2024

Abstract Deuterium labeling compounds play a crucial role in organic and pharmaceutical chemistry. The synthesis of such typically involves deuterated building blocks, allowing for the incorporation deuterium atoms functional groups into target molecule single step. Unfortunately, limited availability synthetic approaches to synthons has impeded progress this field. Here, we present an approach utilizing alkyl-substituted thianthrenium salts that efficiently selectively introduce at α position alkyl chains through pH-dependent HIE process, using D 2 O as source. resulting α-deuterated salts, which bear two atoms, exhibit excellent selectivity electrophilic substitution reactions. Through situ formation isotopically labelled halides, these demonstrate compatibility series metallaphotoredox cross-electrophile coupling with (hetero)aryl, alkenyl, bromides, other salts. Our technique allows wide range substrates, high incorporation, precise control over site insertion within benzyl position, allylic or any chain between, well neighboring heteroatoms. This makes it invaluable synthesizing various deuterium-labeled compounds, especially those significance.

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

141
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

86
Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions DOI
Yaowen Liu, Pengfei Li, Yanwei Wang

et al.

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

Published: June 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Language: Английский

Citations

86
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

75
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

61
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
Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source DOI
Cuibo Liu, Yongmeng Wu, Bo‐Hang Zhao

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(13), P. 1872 - 1883

Published: June 14, 2023

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic by using water (H2O) as hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid use high-pressure flammable gas or other toxic/expensive donors, which usually cause environmental, safety, cost concerns. Interestingly, utilizing easily available heavy (D2O) for deuterated syntheses also attractive due widespread applications molecules synthesis pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, how electrodes dictate outcomes remains elusive. Therefore, rational design nanostructured driving electrocatalytic series organics via H2O electrolysis developed.In this Account, we review recent advances different types functional groups, including C≡C, C≡N, C═C, C═O, C-Br/I bonds, -NO2, N-heterocycles, with over cathodes. First, general steps (reactant/intermediate adsorption, active atomic (H*) formation, surface reaction, product desorption) are analyzed, key factors proposed optimize performance (e.g., selectivity, activity, Faradaic efficiency (FE), rate, productivity) inhibit side reactions. Then, ex situ spectroscopic tools study intermediates interpret mechanisms introduced. Third, based knowledge mechanisms, introduce catalyst principles detail adoption reactants intermediates, promote formation H* from electrolysis, evolution reactions, improve FEs, space-time productivity products. We then some typical examples. (i) P- S-modified Pd decrease C═C adsorption enabling semihydrogenation alkynes high selectivity FEs at lower potentials. creating high-curvature nanotips concentrate substrates further speeds up process. (ii) By introducing low-coordination sites into Fe combining fluorine modify Co facilitate nitriles N-heterocycles activity obtained. (iii) forming isolated induce specific σ-alkynyl steering S vacancies Co3S4-x preferentially adsorb reduced group-decorated nitroarenes chemoselectivity realized. (iv) For reactant participated designing hydrophobic diffusion layer-supported ultrasmall Cu nanoparticles enhance mass transfer, activation, H2 ethylene ampere-level production 97.7% FE accomplished. Finally, provide outlook current challenges promising opportunities area. believe that summarized here paradigm highly selective nanomaterials achieve fascinating performances.

Language: Английский

Citations

54
Electrochemical radical-polar crossover: a radical approach to polar chemistry DOI

Zhoumei Tan,

Haonan Zhang, Kun Xu

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 450 - 470

Published: Nov. 3, 2023

Language: Английский

Citations

50
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