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

---

Organic Electrochemistry: Molecular Syntheses with Potential

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

---

Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

---

Powering the Future: How Can Electrochemistry Make a Difference in Organic Synthesis?

Chem, Journal Year: 2020, Volume and Issue: 6(10), P. 2484 - 2496

Published: Sept. 24, 2020

Language: Английский

---

Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

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

---

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

---

Manganese-Catalyzed Oxidative Azidation of C(sp³)–H Bonds under Electrophotocatalytic Conditions

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(41), P. 17693 - 17702

Published: Sept. 17, 2020

The selective installation of azide groups into C(sp3)-H bonds is a priority research topic in organic synthesis, particularly pharmaceutical discovery and late-stage diversification. Herein, we demonstrate generalized manganese-catalyzed oxidative azidation methodology using nucleophilic NaN3 as an source under electrophotocatalytic conditions. This approach allows us to perform the reaction without necessity adding excess substrate successfully avoiding use stoichiometric chemical oxidants such iodine(III) reagent or NFSI. A series tertiary secondary benzylic C(sp3)-H, aliphatic drug-molecule-based substrates are well tolerated our protocol. simultaneous gram-scale synthesis ease transformation amine collectively advocate for potential application preparative synthesis. Good reactivity bond selectivity incorporate nitrogen-based functionality at alkyl group also provide opportunities manipulate numerous medicinal candidates. We anticipate synthetic protocol, consisting metal catalysis, electrochemistry, photochemistry, would new sustainable option execute challenging transformations.

Language: Английский

---

Nitrogen-Centered Radicals in Functionalization of sp² Systems: Generation, Reactivity, and Applications in Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(9), P. 8181 - 8260

Published: March 14, 2022

The chemistry of nitrogen-centered radicals (NCRs) has plentiful applications in organic synthesis, and they continue to expand as our understanding these reactive species increases. utility intermediates is demonstrated the recent advances C–H amination (di)amination alkenes. Synthesis previously challenging structures can be achieved by efficient functionalization sp2 moieties without prefunctionalization, allowing for faster more streamlined synthesis. This Review addresses generation, reactivity, application NCRs, including, but not limited to, iminyl, aminyl, amidyl, aminium species. Contributions from early discovery up most examples have been highlighted, covering radical initiation, thermolysis, photolysis, and, recently, photoredox catalysis. Radical-mediated intermolecular (hetero)arenes occur with a variety complex amine precursors, generating aniline derivatives, an important class drug development. Functionalization olefins achievable high anti-Markovnikov regioselectivity allows access difunctionalized when intermediate carbon are trapped. Additionally, reactivity NCRs harnessed rapid construction N-heterocycles such pyrrolidines, phenanthridines, quinoxalines, quinazolinones.

Language: Английский

---

Non-innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(29), P. 10882 - 10889

Published: July 13, 2021

We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of an isophthalonitrile photocatalyst and sodium formate promotes diverse aryl coupling reactions abundant but difficult to reduce chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled key terminal reductant byproduct, carbon dioxide anion.

Language: Английский

---

Electrophotocatalysis: Combining Light and Electricity to Catalyze Reactions

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12567 - 12583

Published: July 11, 2022

Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions that have received tremendous attention in recent years. In contrast, processes combine these modalities, an area termed electrophotocatalysis, until recently remained quite rare. However, over past several years a number reports this shown potential combining power light electrical energy to realize new catalytic transformations. Electrophotocatalysis offers ability perform photoredox without need large quantities stoichiometric or superstoichiometric oxidants reductants by making use electrochemical as electron source sink. addition, electrophotocatalysis is readily amenable generation open-shell photocatalysts, which tend exceptionally strong redox potentials. way, potent yet selective been realized under relatively mild conditions. This Perspective highlights advances provides some possible avenues future work growing area.

Language: Английский

---