Efficient Electrocatalysis for the Preparation of (Hetero)aryl Chlorides and Vinyl Chloride with 1,2‐Dichloroethane

Liang, Yujie; Lin, Fengguirong; Adeli, Yeerlan; Jin, Rui; Jiao, Ning

doi:10.1002/ange.201814570

Cited by 25 publications

(9 citation statements)

References 59 publications

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“…Using this procedure, a series of mono-substituted, di-substituted and tri-substituted alkenes participated smoothly in the 1,2-transfer dichlorination reaction, with free alcohol (29, 35, and 37), ester (30), imide (32), phosphonate (33), sulfone (34), and Ts and Boc protected amine moieties (38 and 39) proving compatible. An internal alkyne (37) was even partially compatible with the reaction conditions, despite the minor formation of unidentified by-products. Various styrene-derived alkenes were converted to the corresponding 1,2-dichlorides in good to excellent yield (42)(43)(44)(45)(46)(47)(48)(49)(50)(51)(52), leaving the Br, Cl, CN, CF3, CHO, and COOH functional groups untouched.…”

Section: Main Textmentioning

confidence: 86%

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Dong

Roeckl

Waldvogel

et al. 2021

Science

172

113

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Vicinal dibromides and dichlorides are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that are traditionally synthesized using hazardous elemental chlorine and bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions that can be used both to synthesize useful dihalogenated molecules from simple alkenes and to recycle waste material through retro-dihalogenation. The reaction is demonstrated using 1,2-dibromoethane, as well as 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, to dibrominate or dichlorinate, respectively, a wide range of alkenes in a simple setup with inexpensive graphite electrodes. Conversely, the hexachlorinated persistent pollutant lindane could be fully dechlorinated to benzene in soil samples using simple alkene acceptors.

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Section: Main Textmentioning

confidence: 86%

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Dong

Roeckl

Waldvogel

et al. 2021

Science

172

113

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“…5,6 As shown in Scheme 1, electrochemical dechlorination of DCE was mainly achieved by β-elimination in a nonaqueous solvent, 7,8 resulting in the formation of highly valuable products, including ethylene, vinyl chloride, hydrogen chloride, and hydrogen. 9,10 This transformation looks promising for industrial production and environmental protection. However, the one-stone-two-birds reaction is difficult to achieve in a practical application due to the vague dechlorination mechanism and unsatisfactory product selectivity.…”

Section: ■ Introductionmentioning

confidence: 99%

Identification of Catalytic Active Sites in Nitrogen-Doped Carbon for Electrocatalytic Dechlorination of 1,2-Dichloroethane

Gan

Wang

et al. 2019

ACS Catal.

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Nitrogen (N)-doped carbon materials are considered as the most promising alternative to replace noble-metal catalysts for electrocatalytic dechlorination of 1,2-dichloroethane (DCE), which is a promising reaction for industrial production and environmental protection. Unfortunately, the vague cognition of the catalytic active sites limits its further development. Herein, a series of surface N-doped porous carbon materials with adjustable N dopants were synthesized to identify the active sites for electrocatalytic dechlorination of DCE. The as-prepared catalyst showed fascinating DCE electrocatalytic dechlorination activity and ethylene selectivity at −2.75 V (vs SCE) with a current density of 17.94 mA cm–2 geometry and ethylene Faradaic efficiency of 21%. The post hydrogen treatment and X-ray photoelectron spectroscopic analysis experimentally proved that the oxidized N acts as the active site for the dechlorination of DCE to CH2CH2, which was further theoretically confirmed by first-principles calculations. This work would open avenues for the development of N-doped carbon and the production of ethylene in an efficient and environmentally benign manner.

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“…125 equiv.) was used as the solvent 34 . While this procedure was efficient for a wide set of terminal alkenes (28-34, Fig.…”

Section: Fig 1 │ Reaction Design and Challenges Of Transfer Difunctionalizationmentioning

confidence: 99%

Merging Shuttle Reactions and Paired Electrolysis: E-Shuttle Unlocks Reversible Halogenations

Dong¹,

Röckl²,

Waldvogel³

et al. 2020

Preprint

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<p>Polyhalogenated molecules have found widespread applications as flame retardants, pest-control agents, polymers and pharmaceuticals. They also serve as versatile synthetic intermediates in organic chemistry due to the inherent reactivity of carbon-halogen bonds. Despite these attractive features, the preparation of polyhalogenated molecules still mainly relies on the use of highly toxic and corrosive halogenating reagents, such as Cl<sub>2</sub> and Br<sub>2</sub>, which are hazardous compounds to transport, store, and handle. Moreover, the use of such highly reactive reagents inherently makes the development of the reverse reactions, <i>retro</i>-dihalogenations, highly challenging, despite their potential for the recycling of persistent halogenated pollutants. Here, we introduce an electrochemically-assisted shuttle<i> (e-shuttle)</i> paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions which can be used both to synthesize useful polyhalogenated molecules from simple alkenes and to recycle waste material through <i>retro</i>-dihalogenation. The power of this reaction is best highlighted by an example, in which different soils contaminated with a persistent environmental pollutant (Lindane), could be directly used as Cl<sub>2</sub>-donors for the transfer dichlorination of simple feedstock alkenes, merging a recycling process with a synthetically relevant dichlorination reaction. We further demonstrate that this paired electrolysis-enabled shuttle protocol, which uses a simple setup and inexpensive electrodes, is applicable to four different, synthetically useful transfer halogenation reactions, and can be readily scaled-up to a decagram scale. In a broader context, the symbiotic merging of shuttle reactions and electrochemistry introduced in this work opens new horizons for safer transfer functionalization reactions that will address important challenges across the molecular sciences.</p> <div><br><div> </div> </div>

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Efficient Electrocatalysis for the Preparation of (Hetero)aryl Chlorides and Vinyl Chloride with 1,2‐Dichloroethane

Cited by 25 publications

References 59 publications

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Identification of Catalytic Active Sites in Nitrogen-Doped Carbon for Electrocatalytic Dechlorination of 1,2-Dichloroethane

Merging Shuttle Reactions and Paired Electrolysis: E-Shuttle Unlocks Reversible Halogenations

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