Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Language: Английский

---

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2017 - 2291

Published: Nov. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Language: Английский

---

Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(3), P. 3180 - 3218

Published: Nov. 19, 2021

Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis been popular improving selectivity and efficiency a wide variety of energy-related applications, last two decades, there much interest to develop conceptually novel transformations, selective functionalization, sustainable reactions. This review discusses recent advances combination electrochemistry homogeneous transition-metal catalysis synthesis. The enabling mechanistic studies are presented alongside advantages as well future directions address challenges metal-catalyzed electrosynthesis.

Language: Английский

---

Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts

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

Published: July 13, 2021

Language: Английский

---

New Bisoxazoline Ligands Enable Enantioselective Electrocatalytic Cyanofunctionalization of Vinylarenes

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(37), P. 14480 - 14485

Published: Sept. 9, 2019

In contrast to the rapid growth of synthetic electrochemistry in recent years, enantioselective catalytic methods powered by electricity remain rare. this work, we report development a highly method for electrochemical cyanophosphinoylation vinylarenes. A new family serine-derived chiral bisoxazolines with ancillary coordination sites were identified as optimal ligands.

Language: Английский

---

Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(2), P. 165 - 178

Published: March 29, 2021

There is a resurgence of interests in organic electrochemistry, which generally accepted as green synthetic tool. In this context, many electrochemical methods have been developed the past decade to access various nitrogen-centered radicals (NCRs) from readily available precursors controlled fashion, enabling rapid development NCR-mediated new reactions for construction nitrogen-containing compounds. review, recent advances chemistry electrochemically generated NCRs are critically highlighted, based on strategies their formation and types NCRs. Focus put mechanism generation different applications.

Language: Английский

---

Exploiting the Marcus inverted region for first-row transition metal–based photoredox catalysis

Science, Journal Year: 2023, Volume and Issue: 382(6667), P. 191 - 197

Published: Oct. 12, 2023

Second- and third-row transition metal complexes are widely employed in photocatalysis, whereas earth-abundant first-row metals have found only limited use because of the prohibitively fast decay their excited states. We report an unforeseen reactivity mode for productive photocatalysis that uses cobalt polypyridyl as photocatalysts by exploiting Marcus inverted region behavior couples increases excited-state energies with increased lifetimes. These (III) can engage bimolecular virtue strong redox potentials sufficiently long lifetimes, catalyzing oxidative C(sp2)-N coupling aryl amides challenging sterically hindered boronic acids. More generally, results imply chromophores be designed to increase lifetimes while simultaneously increasing energies, providing a pathway relatively abundant photoredox catalysts.

Language: Английский

---

Active site-directed tandem catalysis on CuO/VO-MnO2 for efficient and stable catalytic ozonation of S-VOCs under mild condition

Nano Today, Journal Year: 2020, Volume and Issue: 35, P. 100944 - 100944

Published: Aug. 26, 2020

Language: Английский

---

Time-Resolved EPR Revealed the Formation, Structure, and Reactivity of N-Centered Radicals in an Electrochemical C(sp³)–H Arylation Reaction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(49), P. 20863 - 20872

Published: Dec. 1, 2021

Electrochemical synthesis has been rapidly developed over the past few years, while a vast majority of reactions proceed through radical pathway. Understanding properties intermediates is crucial in mechanistic study electrochemical transformations and will be beneficial for developing new reactions. Nevertheless, it rather difficult to determine "live" due their high reactivity. In this work, formation structure sulfonamide N-centered radicals have researched directly by using time-resolved electron paramagnetic resonance (EPR) technique under conditions. Supported EPR results, reactivity as mediator hydrogen atom transfer (HAT) approach discussed. Subsequently, these results successfully utilized discovery an unactivated C(sp3)–H arylation reaction. The kinetic experiments revealed rate-determined step anodic oxidation sulfonamides.

Language: Английский

---

Nickela‐electrocatalyzed C−H Alkoxylation with Secondary Alcohols: Oxidation‐Induced Reductive Elimination at Nickel(III)

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(8), P. 3178 - 3183

Published: Nov. 15, 2019

Abstract Nickela‐electrooxidative C−H alkoxylations with challenging secondary alcohols were accomplished in a fully dehydrogenative fashion, thereby avoiding stoichiometric chemical oxidants, H 2 as the only byproduct. The nickela‐electrocatalyzed oxygenation proved viable various (hetero)arenes, including naturally occurring alcohols, without racemization. Detailed mechanistic investigation, DFT calculations and cyclovoltammetric studies of well‐defined activated nickel(III) intermediate, suggest an oxidation‐induced reductive elimination at nickel(III).

Language: Английский

---