Synthetic utilization of electrogenerated bases, I - Michael reactions

Baizer, Manuel M.; Chruma, John L.; White, D. A.

doi:10.1016/s0040-4039(01)87666-8

Cited by 31 publications

(19 citation statements)

References 10 publications

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“…Considerable quantities of the dibromomalonate ester were formed even at low conversions, which would give rise to large amounts of either (III) or (IV) in the undivided cell, even at low conversions, as is observed Oxidation of methanol and ethanoL--Electrolysis of refluxing methanol containing sodium iodide in an undivided cell with either graphite or platinum electrodes led to a smooth reaction giving methyl formate in ca. In this latter experiment methyl formate was 4CH3ONa + 212--> HCOOCHa -t-4NaI -t-2CH3OH [19] detected by GLC/mass spectroscopy. Presumably, it is formed via formaldehyde (Eq.…”

Section: [9]mentioning

confidence: 78%

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Syntheses with Electrogenerated Halogens: Part II . Oxidation of Malonate Esters

White

1977

J. Electrochem. Soc.

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The indirect electrochemical oxidation of malonate esters (I) to ethane-1,1,2,2-tetracarboxylate esters (II) has been investigated in greater detail than previously reported. With acetonitrile or an alcohol as the solvent, ethenetetracarboxylate (III), propane-l,l,2,2,3,3-hexacarboxylate (IV), and ethane-1,1,2-tricarboxylate (V) esters were also formed. If the conversion of (I) was limited to 70%, by-product formation was low and 98% yields of (II) were obtained. In acetonitrile, current efficiency was comparable with the chemical yield, but with alcoholic solvents it was lower (70-80%) due to competing indirect oxidation of the alcohol to the corresponding alkyl formate (VI). The similar coupling of monosubstituted malonate esters (VII; giving VIII) shows a marked steric effect similar to that observed in some cyanoethylation reactions, suggesting that the coupling occurs via a nucleophilic displacement reaction. The steric effect rationalizes the absence of tetrameric and higher products. The similar cyclization of some bismalonate esters (IX; giving X) is also reported.

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Section: [9]mentioning

confidence: 78%

“…It was observed in a divided cell experiment that the malonate esters (Ia and Ib) were readily brominated by anodically generated bromine, whereas they did not react with iodine generated in the same way. [19]). 65% .current efficiency.…”

Section: [9]mentioning

confidence: 99%

Syntheses with Electrogenerated Halogens: Part II . Oxidation of Malonate Esters

White

1977

J. Electrochem. Soc.

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“…The first electrochemically induced Michael reactions were performed in the 1970s by Baizer et al 13,14. at a controlled electrode potential in a divided cell (Scheme ).…”

Section: Electrochemically Induced Reactions Of Ch Acids With Activamentioning

confidence: 99%

“…The reactions are generally initiated by the radical anion of the activated alkene, as CH acids are usually reduced at a more negative potential14 (Scheme ).…”

Section: Electrochemically Induced Reactions Of Ch Acids With Activamentioning

confidence: 99%

“…The first cascade electrochemically induced chain reactions in a divided cell were accomplished as a Michael addition with further cyclization14 (Scheme ), and as two electrogenerated base‐initiated sequential Michael additions to form 2 : 1 linear adducts;17a–17c in the second case, fullerene C 60 was used as the mediator (Scheme ).…”

Section: Electrochemically Induced Reactions Of Ch Acids With Activamentioning

confidence: 99%

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