Quantitative studies in stereochemistry. Photochemistry. VII. Electrochemistry. 4. Photochemical and electrochemical bimolecular reduction of aldehydes and unsymmetrical ketones. Common stereochemistry

Stocker, Jack H.; Jenevein, Roy M.

doi:10.1021/jo01262a002

Cited by 31 publications

(11 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In acidic medium, as previously reported by Stocker et al (22), electrolysis at the first reduction step A, (Eappl (Al) = -1.05 V) yields pinacols ( Table 3). The ketyl radical results from the reduction of the protonated ketone (wave A, in Fig.…”

Section: Discussionsupporting

confidence: 81%

“…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). In aqueous solution, it has been reported that the successive reductive removal of the three fluorine atoms of trifluoromethyl compounds can be carried out at a single potential (-1.7 V in the case of TFMA) (8,9,13).…”

Section: C-ohsupporting

confidence: 90%

“…However, when the proton concentration decreases, the electropinacolization involving radical-radical, radical-substrate, or ion-substrate coupling (22,23) becomes prevalent with, as a consequence, a decrease of the wave height (i,,) (Fig. 1).…”

Section: C-ohmentioning

confidence: 99%

See 2 more Smart Citations

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Liotier¹,

Mousset²,

Mousty³

1995

Can. J. Chem.

View full text Add to dashboard Cite

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.

show abstract

Section: Discussionsupporting

confidence: 81%

Section: C-ohsupporting

confidence: 90%

See 1 more Smart Citation

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Liotier¹,

Mousset²,

Mousty³

1995

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…[15] The d,l/meso ratio of 9.5 for the two diastereomeric pinacols 7 is quite high. Bewick et al [16,17] and Stocker et al [18,19] have postulated that this diastereoselectivity can be explained by ion-pair formation between the anion-radical and BuN ϩ from the supporting electrolyte. Thereby the less hindered radical pair with the methyl and phenyl groups facing each other (Scheme 2) leads to the favoured d,l diatereiosomer.…”

Section: Electrolysis Of the Model Compoundmentioning

confidence: 99%

“…[18,19] This shift can be explained by a solvation of the anion rad- icals by the hydroxyl groups of the carbohydrate that competes with the ion pair formation by BuN ϩ . The steric interactions of the carbohydrate groups promote a head-to-tail orientation of the two anion-radicals.…”

Section: Electrolysis Of the Glycosidic Ketones 1 Andmentioning

confidence: 99%

Electrochemical Reduction in an Aprotic Medium of New Functionalized Amphiphilic Molecules Derived from Sugars: Stereoselective Pinacolization and an Example of a Glycosidic Carbon-Oxygen Bond Cleavage

Maurice¹,

Schöllhorn²,

Canet³

et al. 2000

Eur. J. Org. Chem.

View full text Add to dashboard Cite

Electroreducible amphiphilic aromatic ketones derived from D‐glucose and D‐glucofuranurono‐6,3‐lactone (D‐glucurone) have been synthesized by Schmidt condensation and reaction of the unprotected lactone with the appropriate substrates, respectively. The macroscale electrolyses of the glucose derivatives, performed in an aprotic solvent (DMF), yield the pinacols possessing two glycosidic side chains. Under the same conditions of electrolysis with the D‐glucurone derivative, the glyosidic carbon‐oxygen bond is cleaved. The use of a redox mediator (couple anthracene−•/anthracene) has demonstrated that a glucosidic bond can be reduced by a homogeneous electron transfer. In the presence of a proton donor the expected D‐glucuronic pinacol is obtained. The radical‐radical coupling involves the formation of two chiral centers. The diastereo‐ and the enantioselectivity of the reaction have been studied by 1H‐ and 2H‐NMR spectroscopy, respectively.

show abstract

Selectivity in Electrochemical Reactions

Nonaka

Schäfer

2004

Encyclopedia of Electrochemistry

View full text Add to dashboard Cite

The sections in this article are Introduction Regioselectivity Regioselectivity at the Anode Regioselective Substitution of CH Bonds Regioselective Addition to Double Bonds Anodic Cleavage Anodic C , C ‐Coupling Regioselectivity in Cathode Reactions Regioselective Substitution Cathodic Addition Cathodic Cleavage Cathodic Coupling Electrogenerated Bases Chemoselectivity General Chemoselectivity in Anode Reactions Anodic Dehydrogenation Anodic Cleavage Anodic Substitution and Addition Chemoselectivity in Cathode Reactions Cathodic Hydrogenation Cathodic Cleavage and Elimination Stereoselectivity General Diastereoselectivity Diastereoselectivity at the Anode Diastereoselectivity at the Cathode Hydrogenation Cleavage Elimination Enantioselectivity General Anode Cathode

show abstract

Quantitative studies in stereochemistry. Photochemistry. VII. Electrochemistry. 4. Photochemical and electrochemical bimolecular reduction of aldehydes and unsymmetrical ketones. Common stereochemistry

Cited by 31 publications

References 2 publications

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Electrochemical and spectroscopic behavior of trifluoromethylacetophenone in aqueous and micellar medium

Electrochemical Reduction in an Aprotic Medium of New Functionalized Amphiphilic Molecules Derived from Sugars: Stereoselective Pinacolization and an Example of a Glycosidic Carbon-Oxygen Bond Cleavage

Selectivity in Electrochemical Reactions

Contact Info

Product

Resources

About