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

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
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

28
Recent Advances in the Electrochemical Defluorinative Transformations of C—F Bonds DOI

Qinhui Wan,

Ruixue Liu, Zhongyi Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(16), P. 1913 - 1928

Published: April 24, 2024

Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.

Language: Английский

Citations

26
Electrochemical generation and utilization of radical intermediates DOI

Zhong‐Wei Hou,

Hai‐Chao Xu, Lei Wang

et al.

Current Opinion in Electrochemistry, Journal Year: 2024, Volume and Issue: 44, P. 101447 - 101447

Published: Jan. 26, 2024

Language: Английский

Citations

22
Electroreduction of unactivated alkenes using water as hydrogen source DOI Creative Commons
Yanwei Wang, Qian Wang, Lei Wu

et al.

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

Published: March 30, 2024

Abstract Herein, we report an electroreduction of unactivated alkyl alkenes enabled by [Fe]-H, which is provided through the combination anodic iron salts and silane generated in situ via cathodic reduction, using H 2 O as H-source. The catalytic amounts Si-additive work H-carrier from to generate a highly active species under continuous electrochemical conditions. This approach shows broad substrate scope good functional group compatibility. In addition hydrogenation, use D instead provides desired deuterated products yields with excellent D-incorporation (up >99%). Further late-stage hydrogenation complex molecules drug derivatives demonstrate potential application pharmaceutical industry. Mechanistic studies are performed provide support for proposed mechanistic pathway.

Language: Английский

Citations

21
Site‐Selective Electrochemical C−H Carboxylation of Arenes with CO2 DOI
Zhiwei Zhao, Yin Liu, Siyi Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Nov. 16, 2022

Herein, a direct, metal-free, and site-selective electrochemical C-H carboxylation of arenes by reductive activation using CO2 as the economic abundant carboxylic source was reported. The electrocarboxylation carried out in an operationally simple manner with high chemo- regioselectivity, setting stage for challenging unactivated (hetero)arenes. robust nature strategy reflected broad scope substrates excellent atom economy unique selectivity. Notably, direct selective various worked well this approach, including electron-deficient naphthalenes, pyridines, phenyl derivatives, substituted quinolines. method benefits from being externally catalyst-free, metal-free base-free, which makes it extremely attractive potential applications.

Language: Английский

Citations

67
Deuterodehalogenation Under Net Reductive or Redox‐Neutral Conditions Enabled by Paired Electrolysis DOI Open Access
Devin Wood, Song Lin

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 4, 2023

Interest in deuterated active pharmaceutical ingredients (APIs) is increasing as deuteration holds promise for kinetic isotope effect (KIE) regulated fine-tuning of API performance. Moreover, deuterium labeling frequently carried out to study organic and bioorganic reaction mechanisms facilitate complex target synthesis. As such, methods highly selective molecules are desirable. Herein, we present an electrochemical method the deuterodehalogenation benzylic halides via a radical-polar crossover mechanism, using inexpensive oxide (D

Language: Английский

Citations

41
Photo- and electro-chemical strategies for the activations of strong chemical bonds DOI
Xianhai Tian, Yuliang Liu, Shahboz Yakubov

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 263 - 316

Published: Dec. 7, 2023

The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)

Language: Английский

Citations

41
Three-Component Cross-Electrophile Coupling: Regioselective Electrochemical Dialkylation of Alkenes DOI
Lingxiang Lu, Yi Wang,

Wendy Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22298 - 22304

Published: Oct. 6, 2023

The cross-electrophile dialkylation of alkenes enables the formation two C(sp

Language: Английский

Citations

32
Photocatalytic Umpolung Strategy for the Synthesis of α-Amino Phosphine Oxides and Deuterated Derivatives DOI
Chunhua Ma, Xiaofeng Li,

Xiya Chen

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(44), P. 8016 - 8021

Published: Oct. 30, 2023

Direct, economical, and green synthesis of deuterated α-amino phosphine oxides remains an elusive challenge in synthetic chemistry. Herein, we report a visible-light-driven umpolung strategy for synthesizing from isocyanide using 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene as the photocatalyst D2O deuterium source. Moreover, streamlined sustainable methodology can be applied modification amino acids, natural products, drugs. The strong antiproliferative activity desired products indicates that method could provide novel privileged scaffold antitumor drug development.

Language: Английский

Citations

29