Dehydrogenative reagent-free annulation of alkenes with diols for the synthesis of saturated O-heterocycles DOI Creative Commons

Chen-Yan Cai,

Hai‐Chao Xu

Nature Communications, Journal Year: 2018, Volume and Issue: 9(1)

Published: Aug. 28, 2018

Abstract Dehydrogenative annulation reactions are among the most straightforward and efficient approach for preparation of cyclic structures. However, applications this strategy synthesis saturated heterocycles have been rare. In addition, reported dehydrogenative bond-forming commonly employ stoichiometric chemical oxidants, use which reduces sustainability brings safety environmental issues. Herein, we report an organocatalyzed electrochemical reaction alkenes with 1,2- 1,3-diols 1,4-dioxane 1,4-dioxepane derivatives. The combination electrochemistry redox catalysis using organic catalyst allows electrosynthesis to proceed under transition metal- oxidizing reagent-free conditions. electrolytic method has a broad substrate scope is compatible many common functional groups, providing access functionalized products diverse substitution patterns.

Language: Английский

Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes DOI
Ruhuai Mei,

Nicolas Sauermann,

João C. A. Oliveira

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(25), P. 7913 - 7921

Published: May 29, 2018

Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations internal alkynes. The electro-oxidative C–H activation manifold proved viable an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant catalysts. electrochemical catalysis prevents the use transition metal oxidants catalysis, generating H2 as sole byproduct. Detailed mechanistic studies provided strong support for facile cobaltation by initially formed cobalt(III) catalyst. subsequent alkyne migratory insertion was interrogated mass spectrometry and DFT calculations, providing formation key seven-membered cobalta(III) cycle regioselective fashion. Key to success unprecedented alkynes represented N-2-pyridylhydrazides, which we developed traceless electrocleavage strategy electroreductive samarium temperature.

Language: Английский

Citations

231
Enantioselective Pallada‐Electrocatalyzed C−H Activation by Transient Directing Groups: Expedient Access to Helicenes DOI Creative Commons
Uttam Dhawa, Cong Tian, Tomasz Wdowik

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(32), P. 13451 - 13457

Published: April 3, 2020

Abstract Asymmetric pallada‐electrocatalyzed C−H olefinations were achieved through the synergistic cooperation with transient directing groups. The electrochemical, atroposelective activations realized high position‐, diastereo‐, and enantio‐control under mild reaction conditions to obtain highly enantiomerically‐enriched biaryls fluorinated N−C axially chiral scaffolds. Our strategy provided expedient access to, among others, novel BINOLs, dicarboxylic acids helicenes of value asymmetric catalysis. Mechanistic studies by experiments computation key insights into catalyst's mode action.

Language: Английский

Citations

231
Recent Advances in Ruthenium(II)‐Catalyzed C−H Bond Activation and Alkyne Annulation Reactions DOI

Gauri Duarah,

Partha Pratim Kaishap, Tahshina Begum

et al.

Advanced Synthesis & Catalysis, Journal Year: 2018, Volume and Issue: 361(4), P. 654 - 672

Published: Aug. 20, 2018

Abstract In the last few decades, transition metal‐catalyzed activation of inert C−H bonds has led to a fundamental change in field synthetic chemistry. Most these reactions deal with simple functionalizations or additions. However, recent years have witnessed an increase bond and annulation reactions. These are appealing organic chemist as they afford highly valuable cyclic compounds rapid sustainable manner from readily available compounds. This review article attempts highlight advances ruthenium alkyne magnified image

Language: Английский

Citations

208
Resource Economy by Metallaelectrocatalysis: Merging Electrochemistry and C H Activation DOI Open Access
Tjark H. Meyer, Lars H. Finger, Parthasarathy Gandeepan

et al.

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(1), P. 63 - 76

Published: March 8, 2019

Language: Английский

Citations

194
3d metallaelectrocatalysis for resource economical syntheses DOI Creative Commons
Parthasarathy Gandeepan, Lars H. Finger, Tjark H. Meyer

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(13), P. 4254 - 4272

Published: Jan. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Language: Английский

Citations

186
Electrophotocatalytic Undirected C−H Trifluoromethylations of (Het)Arenes DOI Creative Commons
Youai Qiu, Alexej Scheremetjew, Lars H. Finger

et al.

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(15), P. 3241 - 3246

Published: Dec. 25, 2019

Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF3 SO2 Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for generation radical. electrophotochemistry was carried out in an operationally simple manner, setting stage challenging trifluoromethylations unactivated arenes heteroarenes. robust nature electrophotochemical manifold reflected by wide scope, including electron-rich electron-deficient benzenes, as well naturally occurring Electrophotochemical further achieved flow modular electro-flow-cell equipped in-operando monitoring unit on-line flow-NMR spectroscopy, providing support single electron transfer processes.

Language: Английский

Citations

174
Recent Advances on the Electrochemical Difunctionalization of Alkenes/Alkynes DOI
Haibo Mei, Zizhen Yin, Jiang Liu

et al.

Chinese Journal of Chemistry, Journal Year: 2019, Volume and Issue: 37(3), P. 292 - 301

Published: Feb. 6, 2019

Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which considered as one the green and efficient methods attracts growing attention. In this review, we summarized comprehensively recent literature reports on electrochemical oxidative difunctionalization unsaturated C—C bonds. The reaction types described review included intermolecular cyclization, intramolecular alkenes/alkynes. This focuses discussion its synthetic generality for preparation functionalized compounds related mechanism.

Language: Английский

Citations

151
Flow Rhodaelectro-Catalyzed Alkyne Annulations by Versatile C–H Activation: Mechanistic Support for Rhodium(III/IV) DOI
Wei‐Jun Kong, Lars H. Finger, Antonis M. Messinis

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(43), P. 17198 - 17206

Published: Sept. 24, 2019

A flow-metallaelectro-catalyzed C–H activation was realized in terms of robust rhodaelectro-catalyzed alkyne annulations. To this end, a modular electro-flow cell with porous graphite felt anode designed to ensure efficient turnover. Thereby, variety C–H/N–H functionalizations proved amenable for annulations high levels regioselectivity and functional group tolerance, viable both an inter- or intramolecular manner. The allowed easy scale up, while in-operando kinetic analysis accomplished by online flow-NMR spectroscopy. Mechanistic studies suggest oxidatively induced reductive elimination pathway on rhodium(III) electrocatalytic regime.

Language: Английский

Citations

146
Mn-Catalyzed Electrochemical Radical Cascade Cyclization toward the Synthesis of Benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one Derivatives DOI
Yong Yuan,

Yongfu Zheng,

Bizhen Xu

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(12), P. 6676 - 6681

Published: May 29, 2020

Benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one derivatives are prevalent in many synthetic intermediates, pharmaceuticals, and organic materials. Herein, we develop a Mn-catalyzed electrochemical radical cascade cyclization reaction that uses electricity as the primary energy input to promote reaction, leading series of benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one under exogenous-oxidant-free conditions. It is worth noting this method can not only realize synthesis but also provides new strategy for generating alkyl radicals from alkylboronic acids.

Language: Английский

Citations

141
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