Asymmetric induction in reduction of acetyl pyridines at a mercury cathode

Kopilov, Jacob; Shatzmiller, S.; Kariv, E.

doi:10.1016/0013-4686(76)85144-4

Cited by 24 publications

(12 citation statements)

References 10 publications

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“…A recent article by Wattanakit described several approaches for the development of chiral metal electrodes for enantioselective recognition and asymmetric synthesis developed over the past decade [18]. Concurrent with pioneering works in the field of asymmetric induction in electrochemical reduction on chiral mercury cathodes in the presence of chiral inductors, including tertiary amines, optically active proteins, and alkaloids [19–20], in 1975, Miller’s group reported the first example of the modification of electrodes via covalent binding [21]. They chemically modified air-oxidized graphite electrodes via treatment with thionyl chloride followed by derivatization with ( S )-(−)-phenylalanine methyl ester.…”

Section: Reviewmentioning

confidence: 99%

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

Ghosh

Shinde

Rueping

2019

Beilstein J. Org. Chem.

173

101

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The direct exploitation of ‘electrons’ as reagents in synthetic organic transformations is on the verge of a renaissance by virtue of its greenness, sustainability, atom economy, step economy and inherent safety. Achieving stereocontrol in such organic electrochemical reactions remains a major synthetic challenge and hence demands great expertise. This review provides a comprehensive discussion of the details of stereoselective organic electrochemical reactions along with the synthetic accomplishments achieved with these methods.

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Section: Reviewmentioning

confidence: 99%

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

Ghosh

Shinde

Rueping

2019

Beilstein J. Org. Chem.

173

101

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“…The transformation resulted in only modest chiral induction and moderate yields, the latter due to competing dimerization of the intermediate coumarin radical. Nevertheless, the organocatalytic strategy inspired the work of other groups working in this field [81][82][83] and chiral amines have been used as additives in catalytic amounts for asymmetric reduction of various ketones, carboxylic acids and oximes as well as for reductive dehalogenation [84][85][86][87][88][89][90][91][92][93][94][95][96][97]. Electrocatalytic reductions have also been carried out using metal catalysts, including a Rh III polypyridyl complex for the hydrogenation of acetophenone with modest chiral induction [98].…”

Section: Reductive Transformationsmentioning

confidence: 99%

Recent Advances in Asymmetric Catalytic Electrosynthesis

Margarita

Lundberg

2020

Catalysts

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The renewed interest in electrosynthesis demonstrated by organic chemists in the last years has allowed for rapid development of new methodologies. In this review, advances in enantioselective electrosynthesis that rely on catalytic amounts of organic or metal-based chiral mediators are highlighted with focus on the most recent developments up to July 2020. Examples of C-H functionalization, alkene functionalization, carboxylation and cross-electrophile couplings are discussed, along with their related mechanistic aspects.

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“…A potentially important approach is that of asvmmetric reduction as a result of addition oP suitable chemical reagents to the solutions being electrolyzed (78) or covalent attachment of such reagents to the electrode surface (79). Thus, addition of alkaloids has been found to induce optical activity in some electrolytic reductions, e.g.…”

Section: Stereospecijic Reductionmentioning

confidence: 99%

Organic electrode processes: generalized reduction mechanisms

Elving¹

1977

Can. J. Chem.

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PHILIP J. ELVING. Can. J. Chem. 55,3392 (1977). Prototype formulations are considered for the reaction pathways commonly encountered for the electrolytic reduction of organic compounds in aqueous and nonaqueous media on the basis that the essential feature is severance of a chemical bond which requires transfer into the reaction site of one or two electrons; multiple electron processes result from instability at the applied potential of initially produced species or their chemically altered products. To obtain electrical neutrality, uptake of electrons may have to be accompanied by that of a cation, generally a proton. Pertinent factors in the path followed in the overall electrode process may include a sequence of free radical or radical anion going to dimeric or carbanion species (depending on the relative rates of chemical and charge-transfer steps), possible interaction of intermediate products with their progenitors, proton donor activities, medium properties (e.g in respect to rates of chemical reactions accompanying charge-transfer and control of the chemical states of reactants and intermediates), stereochemical factors inherent in reactant and intermediate species, and chemical interaction with the electrode material. Application of the general mechanistic considerations are illustrated by various types of electrolytic reductions: aromatic hydrocarbon, nitrogen heterocycle, carbon-halogen bond, ketone carbonyl group, and beta halogenated and/or unsaturated acids. PHILIP J. ELVING. Can. J. Chem. 55,3392 (1977). Des formules modkles sont considerees pour des chemins rkactionnels souvent rencontres dans la reduction tlectrolytique de composks organiques en milieu aqueux et non aqueux. On se base sur le fait que la rupture du lien chimique exige le transfert d'un ou deux Blectrons au site rtactionnel. Les processus multi-electroniques resultent de I'instabilite au potentiel appliquk des espkces initialement produites ou de leurs produits transformks. Afin d'obtenir une neutralitk Blectrique, le transfert d'un Blectron doit &tre accompagne par celui d'un cation, gknkralement un proton. Les facteurs appropriks dans ce chemin rkactionnel suivi, tout au long du processus prenant place aux klectrodes, peut impliquer : (a) la sequence d'un radical libre ou d'un radical anionique donnant des dim&res ou carbanions (dkpendant des vitesses relatives des Btapes chimiques et celles de transfert de charge) ; (b) I'interaction possible des intermkdiaires avec les produits initiaux, (c) des activitks proton-donneur; (d) des propriktes de milieu (i.e. par rapport aux reactions chimiques accompagnant le transfert de charge ainsi que du contrBle des Btats chimiques des rkactifs et intermkdiaires); (e) des facteurs stkrtochimiques propres aux rtactifs et intermkdiaires; (f) l'interaction chimique avec I'klectrode. L'application des considkrations mkcanistiques generales est illustrte par diffkrents types de reduction tlectrolytique, un hydrocarbure aromatique, un hkterocycle contenant un atome d'azote, un lien carbone-haloghe...

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Asymmetric induction in reduction of acetyl pyridines at a mercury cathode

Cited by 24 publications

References 10 publications

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

Recent Advances in Asymmetric Catalytic Electrosynthesis

Organic electrode processes: generalized reduction mechanisms

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