Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors DOI
Luiz F. T. Novaes, Yi Wang, Jinjian Liu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14106 - 14112

Published: Nov. 3, 2022

In this work, we report manganese porphyrin complexes for the electrocatalytic vicinal diazidation of alkenes with sodium azide. This protocol shows improved practicality over our previous work using MnBr2 catalysis in following aspects: (1) it requires substantially lower catalyst loading (as low as 0.3 mol %), which reduces formation metal azide and simplifies product purification; (2) introduction a neutral aqueous buffer prevents generation toxic hydrazoic acid, contributing to safer experimental procedure; (3) catalytic system displays reactivity toward unactivated terminal alkenes. Mechanistic studies support roles second-sphere hydrogen-bond donors stabilizing key reaction intermediates.

Language: Английский

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
Electrocatalytic three-component reactions: synthesis of tellurium-containing oxazolidinone for anticancer agents DOI

Xue‐Qi Zhou,

Haitao Tang, Fei‐Hu Cui

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(13), P. 5024 - 5029

Published: Jan. 1, 2023

A new synthetic method involving electrochemical catalysis were used to synthesize various tellurium-containing oxazolidinones which showed better antitumor activity compared other oxazolidinones.

Language: Английский

Citations

44
Nickel-electrocatalysed C(sp3)–C(sp3) cross-coupling of unactivated alkyl halides DOI
Pengfei Li, Zile Zhu,

Chengcheng Guo

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(4), P. 412 - 421

Published: Feb. 23, 2024

Language: Английский

Citations

30
Regioselective Access to Vicinal Diamines by Metal‐Free Photosensitized Amidylimination of Alkenes with Oxime Esters DOI
Yu Zheng, Zhu‐Jun Wang,

Zhipeng Ye

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 9, 2022

A metal-free photosensitized protocol for regioselective diamination of alkene feedstocks over a single step was developed based on the rationally designed bifunctional reagent, thus affording range differentially protected 1,2-diamines in moderate to high yields. Mechanistic studies reveal that reaction is initiated with triplet-triplet energy transfer between thioxanthone catalyst and followed by fragmentation simultaneously generate long-lived iminyl radical transient amidyl radical. The excellent regioselectivity presumably stems from large reactivity difference two different N-centered species. This characterized regioselectivity, broad functional group tolerance, mild conditions, which would enrich diversity versatility facilitate diversity-oriented synthesis 1,2-diamine-containing complex molecule scaffolds.

Language: Английский

Citations

60
Photochemical diazidation of alkenes enabled by ligand-to-metal charge transfer and radical ligand transfer DOI Creative Commons

Kang‐Jie Bian,

Shih‐Chieh Kao,

David Nemoto

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 23, 2022

Vicinal diamines are privileged synthetic motifs in chemistry due to their prevalence and powerful applications bioactive molecules, pharmaceuticals, ligand design for transition metals. With organic diazides being regarded as modular precursors vicinal diamines, enormous efforts have been devoted developing efficient strategies access diazide generated from olefins, themselves common feedstock chemicals. However, state-of-the-art methods alkene diazidation rely on the usage of corrosive expensive oxidants or complicated electrochemical setups, significantly limiting substrate tolerance practicality these large scale. Toward overcoming limitations, here we show a photochemical alkenes via iron-mediated ligand-to-metal charge transfer (LMCT) radical (RLT). Leveraging merger two reaction manifolds, utilize stable, earth abundant, inexpensive iron salt function both initiator terminator. Mild conditions, broad scope amenability continuous-flow rendering transformation photocatalytic were demonstrated. Preliminary mechanistic studies support nature cooperative process diazidation, revealing this approach be means olefin difunctionalization.

Language: Английский

Citations

52
Electrochemically Mediated Carboxylative Cyclization of Allylic/Homoallylic Amines with CO2 at Ambient Pressure DOI
Yong-Zhou Pan, Qiang Xia,

Jinxiu Zhu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(44), P. 8239 - 8243

Published: Nov. 2, 2022

CO2 is an important C1 resource. We report a method for the synthesis of pharmacologically active 2-oxazolidinones by reacting with allylic amines. As opposed to previous addition reactions, unsaturated double bonds are preserved. Thus, product more plastic and easier use subsequent structural modification. Furthermore, this can also be applied six-membered heterocycles (1,3-oxazinan-2-ones) participation low concentration CO2, indicating it has certain practicability.

Language: Английский

Citations

49
Iron-mediated ligand-to-metal charge transfer enables 1,2-diazidation of alkenes DOI Creative Commons
Muliang Zhang, Jinghui Zhang, Qingyao Li

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 23, 2022

Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well privileged molecular catalysts, an efficient practical strategy that avoids use stoichiometric strong oxidants is highly desirable. We herein report application ligand-to-metal charge transfer (LMCT) excitation to 1,2-diazidation reactions from alkenes TMSN

Language: Английский

Citations

41
Research progress in electrochemical/photochemical utilization of methanol as a C1 source DOI
Haitao Tang, Yong-Zhou Pan, Ying‐Ming Pan

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(21), P. 8313 - 8327

Published: Jan. 1, 2023

This review highlights the recent advances in various electrochemical and photochemical reactions using methanol as a sustainable C1 source.

Language: Английский

Citations

39
Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons DOI Creative Commons
Ping‐Fu Zhong, Jia‐Lin Tu,

Yating Zhao

et al.

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

Published: Oct. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Language: Английский

Citations

37
Electrochemical oxidative difunctionalization of diazo compounds with two different nucleophiles DOI Creative Commons

Dongfeng Yang,

Zhipeng Guan,

Yanan Peng

et al.

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

Published: March 17, 2023

With the fast development of synthetic chemistry, introduction functional group into organic molecules has attracted increasing attention. In these reactions, difunctionalization unsaturated bonds, traditionally with one nucleophile and electrophile, is a powerful strategy for chemical synthesis. this work, we develop different path electrochemical oxidative diazo compounds two nucleophiles. Under metal-free external oxidant-free conditions, series structurally diverse heteroatom-containing hardly synthesized by traditional methods (such as high-value alkoxy-substituted phenylthioacetates, α-thio, α-amino acid derivatives well α-amino, β-amino derivatives) are obtained in synthetically useful yields. addition, procedure exhibits mild reaction excellent functional-group tolerance good efficiency on large-scale Importantly, protocol also amenable to key intermediate bioactive simple practical process.

Language: Английский

Citations

30