Selective Aerobic Oxidation of Benzylic Alcohols Catalyzed by a Dicyclopropenylidene–Ag(I) Complex

Mir, Roya; Rowshanpour, Rozhin; Dempsey, Katie; Pilkington, Melanie; Dudding, Travis

doi:10.1021/acs.joc.9b00624

Cited by 4 publications

(4 citation statements)

References 32 publications

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“…Some effective methodologies have been developed for the oxidation of alcohols and oxidative cleavage of C−C bonds, including β ‐O‐4 linkages using metal‐based catalysts during the past decades [16–51] . Such traditional procedures involve the addition of stoichiometric amounts of oxidants, or metal components like manganese(IV) or chromium(VI) based reagents (Figures 1a and 2a).…”

Section: Introductionmentioning

confidence: 99%

“…In a constant search for cleaner (“greener”) technologies, oxygen is undoubtedly the most ubiquitous, atom‐economical, and environmentally benign oxidant, that produces water as the only by‐product [25] . In recent times, a few other protocols for oxidation/oxidative functionalization of alcohols and C−C bonds utilizing transition metal‐based catalysts [26–51] have been reported (Figures 1b and 2b). Nevertheless, many of the recently evolved methodologies that could use oxygen/air as the sole oxidant suffer from the limitations of either toxic or harsh reaction conditions and require specialized components like noble/bimetallic catalysts, external ligands, free radical additives, and/or common organic solvents.…”

Section: Introductionmentioning

confidence: 99%

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A Metallomicellar Catalyst for Controlled Oxidation of Alcohols and Lignin Mimics in Water using Open Air as Oxidant

Thiruvengetam,

Sunani,

Kumar Chand

2024

ChemSusChem

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Alcohol groups and β‐O‐4 (C‐C) linkages are widespread in biomass feedstock that are abundant renewable resource for value‐added chemicals. The development of sustainable protocols for direct oxidation or oxidative cleavage of feedstock materials in a controlled fashion, using open air as an oxidant is an intellectually stimulating task to produce industrially important value‐added carbonyls. Further, the oxidative depolymerization of lignin into fine chemicals has evoked interest in recent times. Herein, we report the first example of a catalyst system that could activate molecular oxygen from atmospheric air for controlled oxidation and oxidative cleavage/depolymerization of feedstock materials such as alcohols, β‐O‐4 (C‐C) linkages and real lignin in water under open air conditions. The selectivity of carbonyl products is controlled by altering the pH between ~7.0 and ~12.0. The current strategy highlights the non‐involvement of any external co‐catalyst, oxidant, radical additives, and/or destructive organic solvents. The catalyst shows a wide substrate scope and eminent functional group tolerance. The upscaled multigram synthesis using an inexpensive catalyst and easily available oxidant evidences the practical utility of the developed protocol. A plausible mechanism has been proposed with the help of a few controlled experiments, and kinetic and computational studies.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Metallomicellar Catalyst for Controlled Oxidation of Alcohols and Lignin Mimics in Water using Open Air as Oxidant

Thiruvengetam,

Sunani,

Kumar Chand

2024

ChemSusChem

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“…Although cyclopropenium salts are known for the past several decades, their potential as organocatalysts in synthetic transformations has been uncovered only recently . Otherwise, the cyclopropenium salts, especially aminocyclopropenium salts, have been majorly utilized as ionic liquids, polyelectrolytes, ligands in transition-metal or main group chemistry, and as activators/promoters in nucleophilic substitution reactions . While considering the catalytic applications in organic transformations, the tris(dialkylamino)cyclopropenium (TDAC) salts have been found serving as effective phase-transfer catalysts in many fundamental organic transformations .…”

Section: Introductionmentioning

confidence: 99%

Bis(amino)cyclopropenium Ion as a Hydrogen-Bond Donor Catalyst for 1,6-Conjugate Addition Reactions

et al. 2021

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The catalytic application of the bis(amino)cyclopropenium ion has been investigated in conjugate addition reactions. The hydrogen atom, which is attached to the cyclopropene ring of bis(amino)cyclopropenium salts, is moderately acidic and can potentially serve as a hydrogen-bond donor catalyst in some organic transformations. This hypothesis has been successfully realized in the 1,6-conjugate addition reactions of p-quinone methides with various nucleophiles such as indole, 2-naphthol, thiols, phenols, and so forth. The spectroscopic studies (NMR and UV–vis) as well as the deuterium isotope labeling studies clearly revealed that the hydrogen atom (C–H) that is present in the cyclopropene ring of the catalyst is indeed solely responsible for catalyzing these transformations. In addition, these studies also strongly indicate that the C–H hydrogen of the cyclopropene ring activates the carbonyl group of the p-quinone methide through hydrogen bonding.

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“…Additionally, an appropriate catalyst in the oxidation reaction can significantly reduce the need for using detrimental oxidants (Dijksman et al, 2001 ; Rautiainen et al, 2014 ). During the past years, different strategies have been developed for the synthesis of aldehydes and ketones through the oxidation of alcohols with metal catalysts, especially Pd (Verma et al, 2017 ), Ru (Ray et al, 2016 ; Sarmah et al, 2018 ), Ag (Mir et al, 2019 ), Au (Zhan et al, 2018 ), and copper-based (Sasano et al, 2018 ) catalysts, which are limited in scope, have long reaction time, and in most cases low conversion rate ( Table 1 ).…”

Section: Introductionmentioning

confidence: 99%

Fabrication of Fe3O4@PVA-Cu Nanocomposite and Its Application for Facile and Selective Oxidation of Alcohols

2020

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Fe 3 O 4 @PVA-Cu nanocomposite was introduced as an affordable catalyst for selective oxidation of alcohols into various aldehydes and ketones. The synthesized nanocomposite was characterized by applying essential analyses. The peaks that are appeared in FT-IR spectroscopy confirmed the production of the Fe 3 O 4 @PVA-Cu nanocomposite. In addition, EDX analysis proved the presence of oxygen, carbon, iron, and copper elements in the catalyst. Further, TGA analysis showed high thermal stability of the nanocomposite. VSM technique was applied to examine the magnetic property of the nanocomposite. The results demonstrated a high magnetic property in the catalyst, which enables easy separation of it from the reaction solution. TEM and SEM imaging showed the nanoscale size of the particles (~20 nm) in the catalyst. Additionally, XRD data was compatible with that of Fe 3 O 4 nanoparticles. The application of the nanocomposite has been studied in the selective oxidation of alcohols in the presence of acetonitrile as solvent, and hydrogen peroxide as a supplementary oxidizing agent. This technique is remarkably facile and inexpensive. Further, the products showed high yields. In addition, the calculated TON and TOF values indicated the phenomenal efficiency of the nanocomposite in preparation of targeted products.

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Selective Aerobic Oxidation of Benzylic Alcohols Catalyzed by a Dicyclopropenylidene–Ag(I) Complex

Cited by 4 publications

References 32 publications

A Metallomicellar Catalyst for Controlled Oxidation of Alcohols and Lignin Mimics in Water using Open Air as Oxidant

A Metallomicellar Catalyst for Controlled Oxidation of Alcohols and Lignin Mimics in Water using Open Air as Oxidant

Bis(amino)cyclopropenium Ion as a Hydrogen-Bond Donor Catalyst for 1,6-Conjugate Addition Reactions

Fabrication of Fe3O4@PVA-Cu Nanocomposite and Its Application for Facile and Selective Oxidation of Alcohols

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