Catalyzing Electrosynthesis: A Homogeneous Electrocatalytic Approach to Reaction Discovery

Accounts of Chemical Research, Год журнала: 2020, Номер 53(3), С. 547 - 560

Опубликована: Фев. 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

Язык: Английский

---

A Survival Guide for the “Electro-curious”

Accounts of Chemical Research, Год журнала: 2019, Номер 53(1), С. 72 - 83

Опубликована: Дек. 11, 2019

ConspectusThe appeal and promise of synthetic organic electrochemistry have been appreciated over the past century. In terms redox chemistry, which is frequently encountered when forging new bonds, it difficult to conceive a more economical way add or remove electrons than electrochemistry. Indeed, many largest industrial chemical processes are achieved in practical using as reagent. Why then, after so years documented benefits electrochemistry, not widely embraced by mainstream practitioners? Erroneous perceptions that "black box" combined with lack intuitive inexpensive standardized equipment likely contributed this stagnation interest within community. This barrier entry magnified fact can already be accomplished simple reagents even if they less atom-economic. Time has proven sustainability economics strong enough driving forces for adoption electrochemical techniques broader like chemists dabbled age-old technique, our first foray into area was choice but rather through sheer necessity.The unique reactivity old redox-modulating technique must therefore highlighted leveraged order draw field. Enabling bonds forged higher levels chemo- regioselectivity will accomplish goal. doing so, envisioned widespread go beyond supplanting unsustainable mundane reactions development exciting paradigms enable heretofore unimagined retrosynthetic pathways. Whereas rigorous physical principles electroorganic synthesis reviewed elsewhere, often case such summaries leave out pragmatic aspects designing, optimizing, scaling up preparative reactions. Taken together, task setting an reaction, much inventing one, vexing seasoned chemists. Account features format focuses on addressing exact issue context own studies. The graphically rich presentation style pinpoints basic concepts, typical challenges, key insights those "electro-curious" who seek rapidly explore power their research.

Язык: Английский

---

Electro-organic synthesis – a 21^stcentury technique

Chemical Science, Год журнала: 2020, Номер 11(46), С. 12386 - 12400

Опубликована: Янв. 1, 2020

This perspective provides insight into recent electro-organic methods and general trends in this field, opens up prospects for future viewpoints.

Язык: Английский

---

New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry

ACS Central Science, Год журнала: 2020, Номер 6(8), С. 1317 - 1340

Опубликована: Июль 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.

Язык: Английский

---

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

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2487 - 2649

Опубликована: Ноя. 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.

Язык: Английский

---

Making electrochemistry easily accessible to the synthetic chemist

Green Chemistry, Год журнала: 2020, Номер 22(11), С. 3358 - 3375

Опубликована: Янв. 1, 2020

This tutorial bridges an important knowledge gap by providing easily accessible introduction that enables synthetic chemists to explore electrochemistry.

Язык: Английский

---

Reproducibility in Electroorganic Synthesis—Myths and Misunderstandings

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(27), С. 14750 - 14759

Опубликована: Янв. 15, 2021

The use of electric current as a traceless activator and reagent is experiencing renaissance. This sustainable synthetic method evolving into hot topic in contemporary organic chemistry. Since researchers with various scientific backgrounds are entering this interdisciplinary field, different parameters methods reported to describe the experiments. variation can lead problems reproducibility electroorganic syntheses. As an example, such density or electrode distance some cases more significant than often anticipated. Minireview provides guidelines on reporting electrosynthetic data dispels myths about technique, thereby streamlining experimental facilitate reproducibility.

Язык: Английский

---

Bipolar Electrochemistry: A Powerful Tool for Electrifying Functional Material Synthesis

Accounts of Chemical Research, Год журнала: 2019, Номер 52(9), С. 2598 - 2608

Опубликована: Авг. 22, 2019

ConspectusElectrosynthesis is a powerful method for the synthesis of organic, inorganic, and polymeric materials based on electron-transfer-driven reactions at substrate/electrode interface. The use electricity synthetic without need hazardous chemical oxidants reductants recognized as green sustainable method. Other advantages include control reaction selectivity by tuning electrode potentials. A different mode driving electrochemical has recently been proposed, in which bipolar electrodes (BPEs) are available wireless that undergo anodic cathodic simultaneously. Bipolar electrochemistry an old technology garnered renewed attention because interesting features BPEs: (i) nature BPE useful sensors material synthesis; (ii) gradient potential distribution BPEs tool preparation surfaces materials; (iii) electrophoresis effective electrolysis. In addition to these unique features, system only requires small amount supporting electrolyte principle, whereas large necessary conventional electrochemistry. Hence, inherently process materials.In this Account, recent progress electrosynthesis functional summarized. was utilized symmetry breaking produce anisotropic site-selective modification conductive objects electrodeposition electropolymerization. Potential gradients interface have successfully used controllable templates form molecular or materials, potentially applicable high throughput analytical equipment biomimetic materials. electric field drive also induce directed migration charged species. synergetic effects electrolysis were demonstrated obtain various These combinations techniques change methodologies synthesis. Furthermore, fundamental principle infers very amounts system, expected lead new methods organic electrosynthesis.

Язык: Английский

---

Aziridine synthesis by coupling amines and alkenes via an electrogenerated dication

Nature, Год журнала: 2021, Номер 596(7870), С. 74 - 79

Опубликована: Июнь 22, 2021

Язык: Английский

---

Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3–Csp2 coupling

Science, Год журнала: 2022, Номер 376(6591), С. 410 - 416

Опубликована: Апрель 21, 2022

Cross-electrophile coupling (XEC) reactions of aryl and alkyl electrophiles are appealing but limited to specific substrate classes. Here, we report electroreductive XEC previously incompatible including tertiary bromides, chlorides, aryl/vinyl triflates. Reactions rely on the merger an electrochemically active complex that selectively reacts with bromides through 1e

Язык: Английский

---