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

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3180 - 3218

Опубликована: Ноя. 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.

Язык: Английский

---

Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(49), С. 20661 - 20670

Опубликована: Ноя. 24, 2020

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated variety of alkene functionalization reactions, most which proceed via an anodic oxidation pathway. In this report, we further expand the scope electrochemistry reductive alkenes. particular, strategic choice reagents reaction conditions enabled radical-polar crossover pathway wherein two distinct electrophiles can be added across highly chemo- regioselective fashion. Specifically, used strategy intermolecular carboformylation, anti-Markovnikov hydroalkylation, carbocarboxylation alkenes—reactions with rare precedents literature—by means electroreductive generation alkyl radical carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) simple, transition-metal-free display broad substrate good tolerance functional groups. A uniform protocol achieve all three transformations by simply altering medium. development provides new avenue for constructing Csp3–Csp3 bonds.

Язык: Английский

---

Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Год журнала: 2021, Номер 2(2), С. 165 - 178

Опубликована: Март 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.

Язык: Английский

---

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

ACS Catalysis, Год журнала: 2021, Номер 11(12), С. 7513 - 7551

Опубликована: Июнь 9, 2021

Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope this field on several fronts. Strategies for regioselectivity control 1,2-migratory insertion across unsymmetrical internal alkynes, as well direct products anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal recently exploited powerful cascade sequences leading complex polycyclic scaffolds, including development enantioselective processes. Elegant enantiospecific dynamic kinetic resolution methods developed accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds emerged based single-electron transfer (SET) that provided fresh impetus alkyne 1,2-difunctionalization complementary stereoselectivity processes relying 1,2-insertion R–M species. Herein, we discuss most recent advances transition-metal-catalyzed using reagents, categorized according type mechanistic outcome. Emphasis is placed aspects, synthetic utility, limitations, challenges future research.

Язык: Английский

---

Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(16), С. 7206 - 7237

Опубликована: Янв. 1, 2022

This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

Язык: Английский

---

Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

eScience, Год журнала: 2022, Номер 2(3), С. 243 - 277

Опубликована: Апрель 23, 2022

Compared with general redox chemistry, electrochemistry using the electron as a potent, controllable, yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis. With its environmentally benign features gradually being uncovered and studied, electrosynthesis is currently undergoing revival becoming rapidly growing area within synthetic community. Among electrochemical transformations, anodically enabled ones have been far extensively exploited than those driven by cathodic reduction, although both approaches are conceptually attractive. To stimulate development of cathodically reactions, this review summarizes recently developed reductive electrosynthetic protocols, discussing highlighting reaction features, substrate scopes, applications, plausible mechanisms reveal recent trends in area. Herein, reduction-enabled preparative transformations categorized into four types: reduction (1) unsaturated hydrocarbons, (2) heteroatom-containing carbon-based systems, (3) saturated C-hetero or C–C polar/strained bonds, (4) hetero-hetero linkages. Apart from net electroreductive few examples photo-electrosynthesis well paired electrolysis also introduced, which offer opportunities overcome certain limitations improve versatility. The electrochemically driven, transition metal-catalyzed cross-couplings that comprehensively discussed several other reviews not included here.

Язык: Английский

---

Recent Advances in the Electrochemical Defluorinative Transformations of C—F Bonds

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(16), С. 1913 - 1928

Опубликована: Апрель 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.

Язык: Английский

---

Seminormal-BrCH₂CH₂OH-mediated electrochemical epoxidation of unactivated olefins

Green Chemistry, Год журнала: 2024, Номер 26(4), С. 2157 - 2161

Опубликована: Янв. 1, 2024

An electrochemical epoxidation of unactivated olefins with water as the source oxygen has been developed.

Язык: Английский

---

Electrifying green synthesis: recent advances in electrochemical annulation reactions

Green Chemistry, Год журнала: 2020, Номер 22(15), С. 4849 - 4870

Опубликована: Янв. 1, 2020

Herein, electrochemical annulations involving mediators and mediator-free conditions have been discussed. Also, the use of sacrificial electrodes has explored.

Язык: Английский

---

CF₃SO₂Na as a Bifunctional Reagent: Electrochemical Trifluoromethylation of Alkenes Accompanied by SO₂ Insertion to Access Trifluoromethylated Cyclic N‐Sulfonylimines

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(18), С. 7266 - 7270

Опубликована: Фев. 20, 2020

An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois' reagent as a source both CF3 and SO2 under direct anodically oxidative conditions, which two C-C bonds, C-X bonds (N-S S-C), rings were formed single operation. This transformation enabled efficient construction various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials.

Язык: Английский

---