Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides DOI Creative Commons

Yun-Zhao Wang,

Zhenhua Wang, Inbal Lorena Eshel

et al.

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

Published: April 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Language: Английский

Catalyzing Electrosynthesis: A Homogeneous Electrocatalytic Approach to Reaction Discovery DOI
Juno C. Siu, Niankai Fu, Song Lin

et al.

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 53(3), P. 547 - 560

Published: Feb. 20, 2020

Electrochemistry has been used as a tool to drive chemical reactions for over two centuries. With the help of an electrode and power source, chemists are bestowed with imaginary reagent whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds (e.g., F

Language: Английский

Citations

614
Recent advances in copper-catalysed radical-involved asymmetric 1,2-difunctionalization of alkenes DOI
Zhong‐Liang Li,

Guichun Fang,

Qiang‐Shuai Gu

et al.

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 49(1), P. 32 - 48

Published: Dec. 5, 2019

The radical-involved 1,2-difunctionalization of alkenes has developed into a robust tool for preparation complex organic molecules. Despite significant advances in this area, the catalytic asymmetric version still remains challenging task mainly due to difficulty stereocontrol highly reactive radical intermediates. Recently, owing good single-electron transfer ability and coordination with chiral ligands copper catalysts, remarkable achievements alkene difunctionalization have been made via synergistic combination ligands. This tutorial review highlights recent progress copper-catalysed mechanistic scenarios governing stereocontrol, an emphasis on utilization

Language: Английский

Citations

609
Organic Electrochemistry: Molecular Syntheses with Potential DOI Creative Commons
Cuiju Zhu, Nate W. J. Ang, Tjark H. Meyer

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 415 - 431

Published: March 9, 2021

Efficient and selective molecular syntheses are paramount to

Language: Английский

Citations

582
New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry DOI Creative Commons
Jinjian Liu, Lingxiang Lu, Devin Wood

et al.

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(8), P. 1317 - 1340

Published: July 16, 2020

As the breadth of radical chemistry grows, new means to promote and regulate single-electron redox activities play increasingly important roles in driving modern synthetic innovation. In this regard, photochemistry electrochemistry-both considered as niche fields for decades-have seen an explosive renewal interest recent years gradually have become a cornerstone organic chemistry. Outlook article, we examine current state-of-the-art areas electrochemistry photochemistry, well nascent area electrophotochemistry. These techniques employ external stimuli activate molecules imbue privileged control reaction progress selectivity that is challenging traditional chemical methods. Thus, they provide alternative entries known reactive intermediates enable distinct strategies were previously unimaginable. Of many hallmarks, electro- are often classified "green" technologies, promoting reactions under mild conditions without necessity potent wasteful oxidants reductants. This reviews most growth these with special emphasis on conceptual advances given rise enhanced accessibility tools trade.

Language: Английский

Citations

375
Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis DOI
Nicholas E. S. Tay, Dan Lehnherr, Tomislav Rovis

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

Citations

357
Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts DOI
Cong Ma, Ping Fang,

Zhao‐Ran Liu

et al.

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

Citations

293
Enantioselective Radical Reactions Using Chiral Catalysts DOI
Shovan Mondal, Frédéric Dumur, Didier Gigmès

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

Citations

253
Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts? DOI
Francisco Zaera

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(9), P. 8594 - 8757

Published: March 3, 2022

A critical review of different prominent nanotechnologies adapted to catalysis is provided, with focus on how they contribute the improvement selectivity in heterogeneous catalysis. Ways modify catalytic sites range from use reversible or irreversible adsorption molecular modifiers immobilization tethering homogeneous catalysts and development well-defined solid surfaces. The latter covers methods for dispersion single-atom within supports as well complex nanostructures, it includes post-modification materials via processes such silylation atomic layer deposition. All these methodologies exhibit both advantages limitations, but all offer new avenues design specific applications. Because high cost most fact that resulting may limited thermal chemical stability, be best aimed at improving selective synthesis value-added chemicals, incorporated organic schemes, other applications are being explored address problems energy production, instance, greener processes. details each approaches discussed, representative examples provided. We conclude some general remarks future this field.

Language: Английский

Citations

250
Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes DOI
Song Lu, Niankai Fu, Brian G. Ernst

et al.

Nature Chemistry, Journal Year: 2020, Volume and Issue: 12(8), P. 747 - 754

Published: June 29, 2020

Language: Английский

Citations

244
Copper-catalyzed radical relay in C(sp3)–H functionalization DOI
Zuxiao Zhang, Pinhong Chen, Guosheng Liu

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(5), P. 1640 - 1658

Published: Jan. 1, 2022

Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and versatility copper-catalyzed cross-coupling. More importantly, significant progress been achieved asymmetric C-H through judicious ligand design. This tutorial review will highlight advances this rapidly growing area, we hope survey inspire future strategic developments for selective functionalization.

Language: Английский

Citations

228