Electrochemically driven stereoselective approach to <i>syn</i>-1,2-diol derivatives from vinylarenes and DMF

Chung, Da Sol; Park, Steve H.; Lee, Sang Gi; Kim, Hyunwoo

doi:10.1039/d1sc00760b

Cited by 35 publications

(18 citation statements)

References 68 publications

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“…In 2021, Kim and colleagues developed an electrochemically enabled syn -diformyloxylation of alkenes for the synthesis of protected syn -1,2-diol derivatives, using N , N -dimethylformamide (DMF) as an oxygen source in the presence of a stoichiometric amount of CF 3 COOH (Scheme 37). 69 This protocol provided a practical and convenient method for stereoselective diformyloxylation, in which the formyloxy group could easily be converted into a hydroxyl group. It is worth noting that the yield of the target difunctionalization product decreased rapidly with other acids, including HCOOH, CH 3 COOH and HOTf, instead of CF 3 COOH.…”

Section: Alkene-derived Radical Cation-initiated Difunctionalizationmentioning

confidence: 99%

Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

2022

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Section: Alkene-derived Radical Cation-initiated Difunctionalizationmentioning

confidence: 99%

Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

2022

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“…The intermediate E could be detected by gas chromatography–mass spectrometry (GC–MS) analysis (see section 2.5 of the Supporting Information). A nucleophilic displacement of obtained intermediate E by DMF gives intermediate F , followed by hydrolysis to produce the target product 4aaa .…”

mentioning

confidence: 99%

Visible-Light-Induced Decarboxylative Alkylation/Ring Opening and Esterification of Vinylcyclopropanes

et al. 2022

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A visible-light-induced four-component reaction of vinylcyclopropanes, N-(acyloxy)phthalimide esters, N,N-dimethylformamide (DMF), and H2O through an oxidative ring opening of cyclopropane is presented. This procedure provides a new and effective way to construct formate esters. DMF is employed as both a solvent and the source of CHO. This difunctionalization of vinylcyclopropanes shows good functional group tolerance under room temperature. A radical pathway is involved, and carbonyl oxygen of ester originated from water in this transformation.

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“…The reason is significantly lower photostability of 3‐Cl in DMF and acetone as compared to acetonitrile (see the Supporting Information S4). Also, relatively low oxidation potential of DMF ( E ox =2.1 V vs. SCE [22] ) should be taken in account allowing its oxidation by 3 + in its excited state. In nitrobenzene and DMSO, several unidentified by‐products were formed within anaerobic oxidation of 4 a , most likely as a result of radical intermediates interaction with products of nitrobenzene/DMSO reduction.…”

Section: Resultsmentioning

confidence: 99%

Highly Chemoselective Catalytic Photooxidations by Using Solvent as a Sacrificial Electron Acceptor

Obertík

Chudoba

Šturala

et al. 2022

Chemistry A European J

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Catalyst recovery is an integral part of photoredox catalysis. It is often solved by adding another component‐a sacrificial agent‐whose role is to convert the catalyst back into its original oxidation state. However, an additive may cause a side reaction thus decreasing the selectivity and overall efficiency. Herein, we present a novel approach towards chemoselective photooxidation reactions based on suitable solvent‐acetonitrile acting simultaneously as an electron acceptor for catalyst recovery, and on anaerobic conditions. This is allowed by the unique properties of the catalyst, 7,8‐dimethoxy‐3‐methyl‐5‐phenyl‐5‐deazaflavinium chloride existing in both strongly oxidizing and reducing forms, whose strength is increased by excitation with visible light. Usefulness of this system is demonstrated in chemoselective dehydrogenations of 4‐methoxy‐ and 4‐chlorobenzyl alcohols to aldehydes without over‐oxidation to benzoic acids achieving yields up to 70 %. 4‐Substituted 1‐phenylethanols were oxidized to ketones with yields 80–100 % and, moreover, with yields 31‐98 % in the presence of benzylic methyl group, diphenylmethane or thioanisole which are readily oxidized in the presence of oxygen but these were untouched with our system. Mechanistic studies based on UV‐Vis spectro‐electrochemistry, EPR and time‐resolved spectroscopy measurements showed that the process involving an electron release from an excited deazaflavin radical to acetonitrile under formation of solvated electron is crucial for the catalyst recovery.

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Electrochemically driven stereoselective approach to syn-1,2-diol derivatives from vinylarenes and DMF

Abstract: We have developed an electrochemically driven strategy for the stereoselective synthesis of protected syn-1,2-diols from vinylarenes with N,N-dimethylformamide (DMF). The newly developed system obviates the need for transition metal catalysts...

Cited by 35 publications

References 68 publications

Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Visible-Light-Induced Decarboxylative Alkylation/Ring Opening and Esterification of Vinylcyclopropanes

Highly Chemoselective Catalytic Photooxidations by Using Solvent as a Sacrificial Electron Acceptor

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