Quantitative studies in stereochemistry. Electrochemistry. II. The ratio of diastereomeric glycols formed in the electrolytic bimolecular reduction of benzaldehyde and propiophenone

Stocker, Jack H.; Jenevein, Roy M.

doi:10.1021/jo01269a109

Cited by 26 publications

(8 citation statements)

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“…1) ( Table 2). The ratio dllmeso for diastereomeric pinacols is 2, in agreement with the value generally reported for these alkaline media (24). Moreover, under our electrolysis conditions at very negative potential, one may consider a possible C-F. bond cleavage concomitant to the ketone reduction (22).…”

Section: C-ohsupporting

confidence: 90%

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Liotier¹,

Mousset²,

Mousty³

1995

Can. J. Chem.

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The electrochemical behavior of 4-trifluoromethylacetophenone (TFMA) has been studied in aqueous (2 ≤ pH ≤ 10), micellar, and ethanolic solutions using polarographic techniques. A slow hydration process of the carbonyl group has been observed by means of polarography and UV–visible spectrophotometry. Besides the well-known pH dependence of the electroreduction of aromatic ketones, C—F bond cleavages concomitant to the ketone reduction occur under electrolysis conditions in alkaline medium (pH = 10) at a very negative potential (−1.7 V), leading to the formation of 4-methylacetophenone, which is reduced at this potential with formation of the carbinol and of symmetrical and dissymmetrical pinacols. Finally, the reduction of TFMA has been performed in the presence of chiral surfactants in order to test their ability to induce an asymmetric induction. Keywords: 4-trifluoromethylacetophenone, 4-methylacetophenone, electroreduction, micellar medium, chiral surfactants, hydration, C—F bond fission.

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Section: C-ohsupporting

confidence: 90%

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Liotier¹,

Mousset²,

Mousty³

1995

Can. J. Chem.

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“…The resulting products were characterized by GC-MS and NMR-spectroscopy. The comparison of the aliphatic proton signal intensity of an observed product with the total aromatic proton signal intensity resulted in a satisfactory calculation of its amount in the product mixture that was isolated [9,10].The dl methine proton of hydrobenzoin is at higher field than the signal of the corresponding meso compound. The same observations were made upon inspection of the signals due to dl and meso-2,3-diphenylbutane-2,3-diol (the reaction product of acetophenone, the signals are due to the dl and meso methyl groups) [16].…”

Section: Influence Of the Substituentsmentioning

confidence: 99%

Samarium(II) iodide: A diastereoselective reagent for the synthesis of aromatic 1,2‐diol structures — model reactions

Wege

Greiner

1995

Acta Polymerica

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Variation of the reaction conditions for the C-C coupling reaction of aromatic carbonyl compounds to their 1,2-diol structures in the presence of samaraium(I1)-iodide led to different diastereoselectivities. The molar ratio of the starting materials, substituents, and solvent variation had a significant influence on 1,2-diol formation. An interpretation of the observed results is suggested. Sterical demands ofthe active complex and an intramolecular samarium-oxygen interaction could lead to the diastereomer ratio obtained.

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“…89 Although these results were attributed mainly to hydrogen bonding, similar electrodimerization of benzaldehyde did not discriminate between formation of rac or meso isomers. 89,90 This angle is expected to be less than 180° in metal diazenido complexes. 62 Hoffmann has described the bonding in this functional group (generically, M-N-N-H) and found a codependence of the metal-N-N and N-N-H angles.…”

Section: Crystals Of [1-h][alclmentioning

confidence: 99%

Synthesis and Reversible Reductive Coupling of Cationic, Dinitrogen-Derived Diazoalkane Complexes

2009

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A series of cationic diazoalkane complexes [4-RC(6)H(4)C(H)NNMo(N[t-Bu]Ar)(3)][AlCl(4)], [1-R][AlCl(4)] (R = NMe(2), Me, H, Br, CN; Ar = 3,5-C(6)H(3)Me(2)) has been prepared by treatment of the N(2)-derived diazenido complex Me(3)SiNNMo(N[t-Bu]Ar)(3) with 4-RC(6)H(4)CHO and 2 equiv of AlCl(3). The structures of [1-H][AlCl(4)] and [1-NMe(2)][AlCl(4)] were determined by X-ray crystallography. The C-N and N-N stretching modes were identified by a combined IR and Raman spectroscopy study, and other physical properties are discussed in detail. The electrochemical reduction potential for [1-R][AlCl(4)] was shown to be linear with the Hammett sigma parameter. This reduction process forms the C-C bonded dimer, mu-(4-RC(6)H(4)C(H)NN)(2)[Mo(N[t-Bu]Ar)(3)](2), that was characterized by X-ray crystallography for R = H. Possible mechanisms for the formation of this dimer are presented. Both electrochemical investigations and quantum chemical calculations are used to describe the odd-electron complex 4-RC(6)H(4)C(H)NNMo(N[t-Bu]Ar)(3), 1-R, that is an intermediate in the formation of [1-R](2). The C-C bond in [1-R](2) is redox-noninnocent and is broken upon oxidation. This reaction was used to prepare [1-H][A] (A = PF(6)(-), OTf(-)), and possible uses of this property in charge-storage devices are discussed.

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Quantitative studies in stereochemistry. Electrochemistry. II. The ratio of diastereomeric glycols formed in the electrolytic bimolecular reduction of benzaldehyde and propiophenone

Cited by 26 publications

References 0 publications

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Samarium(II) iodide: A diastereoselective reagent for the synthesis of aromatic 1,2‐diol structures — model reactions

Synthesis and Reversible Reductive Coupling of Cationic, Dinitrogen-Derived Diazoalkane Complexes

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