Selective Electrochemical Halogenation of Functionalized Quinolone DOI
Meiqian Hu, Shuai Zhang, Changsheng Qin

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(18), P. 12958 - 12970

Published: Aug. 24, 2023

This work describes an effective C3–H halogenation of quinoline-4(1H)-ones under electrochemical conditions, in which potassium halides serve as both halogenating agents and electrolytes. The protocol provides expedient access to different halogenated with unique regioselectivity, broad substrate scope, gram-scale synthesis employing convenient, environmentally friendly electrolysis, undivided cell. Mechanism studies have shown that halogen radicals can promote the activation N–H bonds quinolones.

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

144
Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

Citations

120
Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds DOI

Qinhui Wan,

Zhongyi Zhang,

Zhong‐Wei Hou

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2830 - 2848

Published: Jan. 1, 2023

Recent advances in the electrochemical generation of 1,3-dicarbonyl radicals from C–H bonds and their mechanistic insights synthetic applications have been summarized.

Language: Английский

Citations

80
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
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
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
Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes DOI
Gang Zhou, Tao Zhou,

Ao‐Lian Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Language: Английский

Citations

20
Catalytic desymmetrization reactions to synthesize all-carbon quaternary stereocentres DOI
Pengwei Xu, Feng Zhou, Lei Zhu

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(11), P. 1020 - 1036

Published: Oct. 16, 2023

Language: Английский

Citations

42
Cobaltaelectro-Catalyzed C–H Annulation with Allenes for Atropochiral and P-Stereogenic Compounds: Late-Stage Diversification and Continuous Flow Scale-Up DOI Creative Commons
Lin Ye, Tristan von Münchow, Lutz Ackermann

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9713 - 9723

Published: July 11, 2023

The 3d metallaelectro-catalyzed C-H activation has been identified as an increasingly viable strategy to access valuable organic molecules in a resource-economic fashion under exceedingly mild reaction conditions. However, the development of enantioselective is very challenging and its infancy. Here, we disclose merger cobaltaelectro-catalyzed with asymmetric catalysis for highly annulation allenes. A broad range C-N axially chiral P-stereogenic compounds were thereby obtained good yields up 98% high enantioselectivities >99% ee. practicality this approach was demonstrated by diversification complex bioactive drug well decagram scale electrocatalysis continuous flow.

Language: Английский

Citations

41
N,O-Auxiliary Enabled Cobaltaelectro-Catalyzed Atroposelective C–H Annulation DOI

Yuanshuo Zhang,

Shuang‐Liang Liu, Tong Li

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 1 - 9

Published: Dec. 7, 2023

Herein, we disclosed an efficient synthesis of C–N axially chiral pyridine-N-oxides through cobalt-catalyzed enantioselective C–H activation and annulation under electro-oxidative conditions. This protocol is accomplished by using a readily available cobalt(II) catalyst salicyloxazoline (Salox) ligand in undivided cell. The combination electrochemical simple Co/Salox system enabled effective control over the chemo- enantioselectivity process. A broad range benzamides alkynes bearing diverse functional groups are well compatible to deliver products with high yields enantioselectivities (up 97% yield 99% ee). scalability, asymmetric application, transformations demonstrated synthetic practicality. Moreover, photoluminescence properties further highlight potential applications this strategy material development performance enhancement.

Language: Английский

Citations

26