Metal-Free Oxidative C=C Bond Cleavage of Electron-Deficient Enamines Promoted by tert-Butyl Hydroperoxide

Adib, Mehdi; Pashazadeh, Rahim; Gohari, Seyed Jamal Adin; Shahsavari, Fatemeh

doi:10.1055/s-0036-1588990

Cited by 6 publications

(2 citation statements)

References 4 publications

(1 reference statement)

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“…This indeed enhances the probability for easy electronic transition that could promote catalysis. Thus, the effective catalytic activity of MOP-Am2 is attributed to the rich delocalization of conjugated π-electrons due to the presence of a nitrogen heteroatom, leading to a strong π···π or C–H···π interaction between the catalyst and styrenes or benzyl alcohols. ,− In effect, it gears up the electron-transfer process between the catalyst and the individual substrate and thereby stimulates catalysis. A similar observation is that an electron-donating group improves styrene conversion and vice versa because of the decrease of the quantitative electric charge on the CC double bond of styrenes.…”

Section: Results and Discussionmentioning

confidence: 99%

Endorsing Organic Porous Polymers in Regioselective and Unusual Oxidative C═C Bond Cleavage of Styrenes into Aldehydes and Anaerobic Benzyl Alcohol Oxidation via Hydride Elimination

Pathak

Khatioda

Sharma

et al. 2021

ACS Appl. Mater. Interfaces

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Oxidative cleavage of styrene CC double bond is accomplished by employing a nitrogen-rich triazine-based microporous organic polymer as an organocatalyst. We report this regioselective reaction as first of its kind with no metal add-ons to afford benzaldehydes up to 92% selectivity via an unusual Wackertype CC bond cleavage. Such a reaction pathway is generally observed in the presence of a metal catalyst. This polymer further shows high catalytic efficiency in an anaerobic oxidation reaction of benzyl alcohols into benzaldehydes. The reaction is mediated by a base via the in situ generation of hydride ions. This study is supported by experiments and computational analyses for a freeradical transformation reaction of oxidative CC bond cleavage of styrenes and a hydride elimination mechanism for the anaerobic oxidation reaction. Essentially, the study unveils protruding applications of metal-free nitrogen-rich porous polymers in organic transformation reactions.

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Section: Results and Discussionmentioning

confidence: 99%

Endorsing Organic Porous Polymers in Regioselective and Unusual Oxidative C═C Bond Cleavage of Styrenes into Aldehydes and Anaerobic Benzyl Alcohol Oxidation via Hydride Elimination

Pathak

Khatioda

Sharma

et al. 2021

ACS Appl. Mater. Interfaces

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“…More recently, Adib et al. reported that enamine oxidation using 2.5 equiv. of tert ‐butyl hydroperoxide (TBHP) in chlorobenzene solvent under heated conditions also produced oxamates.…”

Section: Figurementioning

confidence: 99%

Copper‐Catalysed (Diacetoxyiodo)benzene‐Promoted Aerobic Esterification Reaction: Synthesis of Oxamates from Acetoacetamides

Zhang

Gao

et al. 2018

Adv Synth Catal

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A copper-catalysed (diacetoxyiodo)benzene-promoted aerobic esterification reaction of acetoacetamides was developed for the synthesis of oxamates, which are useful precursors in synthetic organic chemistry. This practical and mild synthetic approach proceeded at 25 8C under open-air conditions and afforded methyl 2-oxo-2-(phenylamino)acetates in good to excellent yields combined with CÀC s-bond cleavage and formal oxidative CÀH bond functionalization. A mechanism is proposed.

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Aerobic Photoredox Catalyzed Oxamate Ester Synthesis from Bromodifluoroacetate Esters

Tagami,

Kawamura,

Sodeoka

2024

Eur J Org Chem

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Here we report an aerobic photoredox catalysis approach to oxamate ester synthesis using bromodifluoroacetate esters and amines under open‐air conditions. Oxamate ester is an important skeleton found in bioactive molecules and used as a synthetic building block. However, previous synthetic methods require the use of moisture‐ and air‐sensitive precursors and/or harsh conditions, limiting accessible oxamate esters. The present method uses bench‐stable bromodifluoroacetate esters and amines under mild photoredox catalytic conditions to furnish a wide variety of oxamate esters. Combining photoredox catalysis with aerobic oxygenation enables the use of bromodifluoroacetate ester as a precursor for the synthesis of oxamate esters via fluoroglyoxylate esters.

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Metal-Free Oxidative C=C Bond Cleavage of Electron-Deficient Enamines Promoted by tert-Butyl Hydroperoxide

Cited by 6 publications

References 4 publications

Endorsing Organic Porous Polymers in Regioselective and Unusual Oxidative C═C Bond Cleavage of Styrenes into Aldehydes and Anaerobic Benzyl Alcohol Oxidation via Hydride Elimination

Endorsing Organic Porous Polymers in Regioselective and Unusual Oxidative C═C Bond Cleavage of Styrenes into Aldehydes and Anaerobic Benzyl Alcohol Oxidation via Hydride Elimination

Copper‐Catalysed (Diacetoxyiodo)benzene‐Promoted Aerobic Esterification Reaction: Synthesis of Oxamates from Acetoacetamides

Aerobic Photoredox Catalyzed Oxamate Ester Synthesis from Bromodifluoroacetate Esters

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