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

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New Bisoxazoline Ligands Enable Enantioselective Electrocatalytic Cyanofunctionalization of Vinylarenes

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(37), С. 14480 - 14485

Опубликована: Сен. 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.

Язык: Английский

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3d metallaelectrocatalysis for resource economical syntheses

Chemical Society Reviews, Год журнала: 2020, Номер 49(13), С. 4254 - 4272

Опубликована: Янв. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Язык: Английский

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Electrophotocatalytic Undirected C−H Trifluoromethylations of (Het)Arenes

Chemistry - A European Journal, Год журнала: 2019, Номер 26(15), С. 3241 - 3246

Опубликована: Дек. 25, 2019

Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF3 SO2 Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for generation radical. electrophotochemistry was carried out in an operationally simple manner, setting stage challenging trifluoromethylations unactivated arenes heteroarenes. robust nature electrophotochemical manifold reflected by wide scope, including electron-rich electron-deficient benzenes, as well naturally occurring Electrophotochemical further achieved flow modular electro-flow-cell equipped in-operando monitoring unit on-line flow-NMR spectroscopy, providing support single electron transfer processes.

Язык: Английский

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Electrochemical Dearomative 2,3-Difunctionalization of Indoles

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(7), С. 2832 - 2837

Опубликована: Янв. 23, 2019

We report the use of electrochemistry to perform a direct oxidative dearomatization indoles leading 2,3-dialkoxy or 2,3-diazido indolines under undivided conditions at constant current. This operationally simple electro-oxidative procedure avoids an external oxidant and displays excellent functional group compatibility. The formation two C-O C-N bonds is believed arise from oxidation into radical cation intermediates.

Язык: Английский

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Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2313 - 2382

Опубликована: Янв. 1, 2022

Visible-light photoredox catalysis has been regarded as an extremely powerful tool in organic chemistry, bringing the spotlight back to radical processes. The versatility of photocatalyzed reactions already demonstrated be effective providing alternative routes for cross-coupling well multicomponent reactions. photocatalyst allows generation high-energy intermediates through light irradiation rather than using highly reactive reagents or harsh reaction conditions. In a similar vein, electrochemistry experienced fruitful renaissance generating without need any catalyst. Such milder approaches pose basis toward higher selectivity and broader applicability. electrochemical reactions, species acts starter cascade events. This diverse reactivity use is usually not covered by classical methods. Owing availability cheaper more standardized photo- reactors, easily scalable flow-setups, it surprising that these two fields have become areas increased research interest. Keeping view, this review aimed at overview synthetic design MCRs involving and/or activation crucial step with particular focus on choice difunctionalized reagent.

Язык: Английский

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Recent Advances on the Electrochemical Difunctionalization of Alkenes/Alkynes

Chinese Journal of Chemistry, Год журнала: 2019, Номер 37(3), С. 292 - 301

Опубликована: Фев. 6, 2019

Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which considered as one the green and efficient methods attracts growing attention. In this review, we summarized comprehensively recent literature reports on electrochemical oxidative difunctionalization unsaturated C—C bonds. The reaction types described review included intermolecular cyclization, intramolecular alkenes/alkynes. This focuses discussion its synthetic generality for preparation functionalized compounds related mechanism.

Язык: Английский

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Electrochemical Oxidative Clean Halogenation Using HX/NaX with Hydrogen Evolution

iScience, Год журнала: 2019, Номер 12, С. 293 - 303

Опубликована: Янв. 27, 2019

Organic halides (R-X) are prevalent structural motifs in pharmaceutical molecules and key building blocks for the synthesis of fine chemicals. Although a number routes available literature organic halides, these methods often require stoichiometric additives or oxidants, metal catalysts, leaving directing groups, toxic halogenating agents. In addition, necessity employing different, tailor-made, catalytic systems each type substrate also limits applicability methods. Herein, we report clean halogenation by electrochemical oxidation with NaX/HX. A series were prepared under catalyst- exogenous-oxidant-free reaction conditions. It is worth noting that this has broad scope; various heteroarenes, arenes, alkenes, alkynes, even aliphatic hydrocarbons could be applied. Most importantly, performed on 200-mmol scale same efficiency (86%, 50.9 g pure product).

Язык: Английский

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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

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Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor

ACS Central Science, Год журнала: 2021, Номер 7(8), С. 1347 - 1355

Опубликована: Авг. 5, 2021

Organic electrochemistry has emerged as an enabling and sustainable technology in modern organic synthesis. Despite the recent renaissance of electrosynthesis, broad adoption synthetic community, especially industrial settings, been hindered by lack general, standardized platforms for high-throughput experimentation (HTE). Herein, we disclose design HT

Язык: Английский

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