Cyclopropane formation by electroreductive coupling of activated olefins and gem-polyhalo compounds

Léonel, Éric; Paugam, Jean Paul; Condon-Gueugnot, Sylvie; Nédélec, Jean‐Yves

doi:10.1016/s0040-4020(98)00059-3

Cited by 22 publications

(10 citation statements)

References 21 publications

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“…The results are listed in Table 1, along with the corresponding yields, either already published or obtained dur-ing this work, obtained by the direct electroreductive coupling previously reported. 1,2 When the activated olefin is less easily reduced than the polychloromethyl compound, or when the two species are reduced at ca. the same potential, we have obtained the best results from the copper-catalysed indirect electrolysis ( Table 1, entries 1 to 9).…”

Section: Methodsmentioning

confidence: 99%

Cyclopropane Formation by Copper-Catalysed Indirect Electroreductive Coupling of Activated Olefins and Activated α,α,α-Trichloro or Gem-Dichloro Compounds

Sengmany¹,

Léonel²,

Paugam³

et al. 2002

Synthesis

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Cyclopropanes have been prepared in good yields by indirect electroreductive coupling of activated olefins and activated a,a,a-trichloro or gem-dichloro compounds (Cl 3 CCO 2 Me, PhCCl 3 , Ph 2 CCl 2 , PhCHCl 2 ). This process, using a copper complex in catalytic amountss is convenient for the reagent couple activated olefin/ activated polyhalide, whatever the reduction potential of each reagent relative to each other. The main advantage of our electrochemical process is that it does not require the use of hazardous, toxic, or not easily prepared reagents like diazocompounds or diazirines.In our ongoing investigation on cyclopropane formation by electroreductive coupling of activated olefins and gemdihalo compounds, we have already reported two successful processes: the direct electroreductive coupling in DMF as solvent using an aluminum rod as the anode, which is efficient when the activated olefin is more easily reducible than the organic gem-dihalide 1 (process a) and the nickel catalysed electroreductive coupling in MeCN as solvent using a Fe/ Ni (64:36) rod as the anode, which applies to unactivated gem-dibromo compounds (dibromomethane, 1,1-dibromoethane, 2,2-dibromopropane) 2 (process b). However, with activated polychloro compounds (methyl trichloroacetate, a,a,a-trichlorotoluene, benzal chloride, dichlorodiphenylmethane) this nickel-catalysed procedure leads to dimerisation and/or reduction of the activated organic polychloride. This led us to further investigations in order to find an alternative system of indirect electrochemical activation applicable to this class of reagents. Saegusa et al 3 reported a cyclopropane synthesis involving a copper-carbenoid isonitrile complex resulting from the oxidative addition of trichloromethyl compounds to a soluble complex of Cu(0)-isonitrile 3 (Scheme 1).We thought it possible to regenerate a catalytic reactive Cu(0) complex by electrochemical reduction of a copper salt in the presence of a more simple ligand than t-BuNC like pyridine, for example. Preliminary experiments were achieved at room temperature in an undivided cell fitted with a Fe rod as the anode, a nickel foam as the cathode, and in the solvent system DMF-pyridine (90:10, v/v). Dimethyl itaconate and dichlorodiphenylmethane were selected as model reagents because all the products of the electrolysis, i.e. methyl 2,2-diphenyl-1-methoxycarbonylmethylcyclopropane-1-carboxylate (1), dimethyl 3-(2,2-diphenylethyl)butane-1,4-dioate (2), diphenylmethane (3), chlorodiphenylmethane (4), and tetraphenylethylene (5) are easily detected by GC. First, a pre-electrolysis involving the reduction of 1 mmole of CuBr (10% versus the limiting reagent) along with the oxidation of the anode was carried out at constant current intensity (0.3 A) during 15 mn. Dimethyl itaconate (10 mmol) and dichlorodiphenylmethane (5 mmol) were then added and the electrolysis was conducted at constant current intensity of 0.1 A until complete consumption of the limiting reagent. During the electrolysis the working-electrode potential was ...

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Section: Methodsmentioning

confidence: 99%

Cyclopropane Formation by Copper-Catalysed Indirect Electroreductive Coupling of Activated Olefins and Activated α,α,α-Trichloro or Gem-Dichloro Compounds

Sengmany¹,

Léonel²,

Paugam³

et al. 2002

Synthesis

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“…The current with the density of 20 mA cm 72 was passed through a DMF solution of activated alkene containing an excess of halo compounds in an undivided cell equipped with a sacrificial aluminium anode and a stainless steel cathode until alkene was completely converted. 26 …”

Section: Scheme 12mentioning

confidence: 99%

Electrochemical synthesis of cyclopropanes

Elinson¹,

Dorofeeva²,

Vereshchagin³

et al. 2015

Russ. Chem. Rev.

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“…Stepwise dechlorination of gem-dichloro-and gem-trichloroalkanes occurs. Dichloromethane can be reduced in the presence of an olefin to form a cyclopropane [25], and reductive coupling of 1,1,1-trichloro-2,2,2-trifluoroethane with aldehydes [26] and of gem-polyhalo compounds with activated olefins [27] is possible. Several studies have involved the electrogeneration of the trichloromethyl anion, which reacts with a number of substrates [28].…”

Section: Halogenated Alkanesmentioning

confidence: 99%

Oxidation and Reduction of Halogen‐containing Compounds

Peters

2004

Encyclopedia of Electrochemistry

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The sections in this article are Introduction Anodic Processes Halogenated Alkanes Alicyclic Halides Aryl Halides Cathodic Processes Halogenated Alkanes Halogenated Alkenes and Alkynes Benzyl Halides Alicyclic Halides Aryl Halides Acyl and Phenacyl Halides Aliphatic α‐Halocarbonyl Compounds Halogenated Heterocyclic Compounds Catalytic Reduction of Carbon–Halogen Bonds

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Cyclopropane formation by electroreductive coupling of activated olefins and gem-polyhalo compounds

Cited by 22 publications

References 21 publications

Cyclopropane Formation by Copper-Catalysed Indirect Electroreductive Coupling of Activated Olefins and Activated α,α,α-Trichloro or Gem-Dichloro Compounds

Cyclopropane Formation by Copper-Catalysed Indirect Electroreductive Coupling of Activated Olefins and Activated α,α,α-Trichloro or Gem-Dichloro Compounds

Electrochemical synthesis of cyclopropanes

Oxidation and Reduction of Halogen‐containing Compounds

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