Electrochemical Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 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.

Язык: Английский

---

Electrochemical radical-polar crossover: a radical approach to polar chemistry

Science China Chemistry, Год журнала: 2023, Номер 67(2), С. 450 - 470

Опубликована: Ноя. 3, 2023

Язык: Английский

---

Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Язык: Английский

---

Electroreductive hydroxy fluorosulfonylation of alkenes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Дек. 13, 2023

An electroreductive strategy for radical hydroxyl fluorosulfonylation of alkenes with sulfuryl chlorofluoride and molecular oxygen from air is described. This mild protocol displays excellent functional group compatibility, broad scope, good scalability, providing convenient access to diverse β-hydroxy sulfonyl fluorides. These fluoride products can be further converted valuable aliphatic fluorides, β-keto β-alkenyl Further, some these showed inhibitory activity against Botrytis cinerea or Bursaphelenchus xylophilus, which could useful potent agrochemical discovery. Preliminary mechanistic studies indicate that this transformation achieved through rapid O2 interception by the alkyl subsequent reduction peroxy radical, outcompete other side reactions such as chlorine atom transfer, hydrogen Russell fragmentation.

Язык: Английский

---

Flow Electroreductive Nickel‐Catalyzed Cyclopropanation of Alkenes Using gem‐Dichloroalkanes

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

Abstract Cyclopropanes are valuable motifs in organic synthesis, widely featured pharmaceuticals and functional materials. Herein, we report an efficient electrochemical methodology for the cyclopropanation of alkenes, leveraging a nickel‐catalyzed process continuous‐flow. The developed protocol demonstrates broad substrate scope, accommodating both electron‐rich electron‐poor alkenes with high group tolerance. Beyond dichloromethane as feedstock methylene source, enables synthesis methylated, deuterated, chloro‐substituted cyclopropanes. Mechanistic investigations suggest electro‐generation nickel carbene key intermediate. Notably, reaction operates under ambient conditions, tolerates air moisture, achieves scalability through continuous‐flow technology, offering straightforward route to multi‐gram quantities enhanced throughput.

Язык: Английский

---

Electrochemical Benzylic C–H Carboxylation

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 9, 2025

Direct benzylic C-H carboxylation stands as a high atom economy, efficient, and convenient route for the synthesis of valuable carboxylic acids, which are great significance in many pharmaceuticals bioactive molecules. However, inherent inertness both bonds carbon dioxide presents challenge further transformations. Herein, we report our efforts to overcome this obstacle via halide-promoted linear paired electrolysis generate various acids. Remarkably, process is transition-metal- base-free, making it environmentally benign cost-effective. Besides, suitable constructing wide range primary, secondary, tertiary acids under mild reaction conditions, demonstrating broad substrate scopes good functional group tolerance. Furthermore, protocol enables direct some drug molecules, including Flurbiprofen, Ibuprofen, Naproxen, facilitates late-stage modification complex compounds, showcasing practical application synthetic chemistry underscores its potential advance related compounds.

Язык: Английский

---

Mechanochemical Synthesis of α‐halo Alkylboronic Esters

Advanced Science, Год журнала: 2024, Номер 11(33)

Опубликована: Июль 3, 2024

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron carbon-halogen bonds into broad range carbon-X allows for programmable bond formation, facilitating the incorporation multiple substituents at single position streamlining synthesis complex molecules. Nevertheless, synthetic potential these compounds is constrained by limited reaction patterns. Additionally, conventional methods often necessitate use bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, involve extended times. In this report, ball milling technique introduced that overcomes limitations, enabling external catalyst-free multicomponent coupling aryl diazonium salts, alkenes, simple halides. This approach offers general straightforward method obtaining diverse array thereby paving way extensive utilization synthons fine chemicals.

Язык: Английский

---

Electrochemical umpolung of C‐H nucleophiles bearing three electron‐withdrawing groups to trigger radical 1,2‐alkylarylations of allylic alcohols

Advanced Synthesis & Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

Abstract The electrochemical catalyst‐free generation of carbon radicals bearing three electron‐withdrawing groups from the corresponding C−H nucleophiles remains unexplored. To this end, we report a direct electro‐oxidation strategy to access these electrophilic under conditions. Enabled by strategy, radical 1,2‐alkylarylations allylic alcohols was realized, affording β ‐quaternary ketones with high functional group compatibility. This protocol is operationally simple and also easy scale up.

Язык: Английский

---

Photocatalyzed Deuterodichloromethylation of Olefins Using Silacarboxylic Acids as Halogen‐Atom Transfer Reagents

European Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Abstract A visible‐light‐induced deuterodichloromethylation of alkenes was developed with readily available and inexpensive deuterochloroform as the reagent. Silacarboxylic acids, which could generate silyl radicals through efficient decarboxylation, were applied halogen atom transfer agents. series deuterium‐containing gem ‐dichloroalkanes prepared in good yields.

Язык: Английский

---

Electrochemical-induced hydrofunctionalizations of alkenes and alkynes

Chemical Synthesis, Год журнала: 2024, Номер 4(1)

Опубликована: Март 1, 2024

The hydrofunctionalizations of readily available alkenes and alkynes are one the most effective useful routes to afford diverse value-added compounds. Although traditional hydrofunctionalization strategies catalyzed by metal catalysts present convenient approaches, they also accompanied resource consumption environmental crisis. Electrosynthesis, as a renewable sustainable technology, has become cost- atom-efficient synthetic route. In this review, electrochemical-induced summarized presented. each section, electrochemical strategy access hydrogenation other (hydroboration, hydrosilylation, hydroalkylation, hydroalkoxylation, hydrocyanation, hydrocarboxylation, etc. ) products elaborated in detail separately. Finally, current challenges prospects for unsaturated carbon‒carbon (C‒C) bonds discussed briefly.

Язык: Английский

---