Dehydrogenation of Perfluoroalkyl Ket­ones by Using a Recyclable Oxoammonium Salt

Hamlin, Trevor A.; Kelly, Christopher B.; Leadbeater, Nicholas E.

doi:10.1002/ejoc.201300392

Cited by 32 publications

(30 citation statements)

References 58 publications

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“…1‐(Nonanyl)‐2,2,2‐trifluoroethanol ( 1a ) and 1‐(β‐phenylethyl)‐2,2,2,‐trifluoroethanol ( 1q ) were also cleanly converted (entries 16 and 17, Table 2). Interestingly, the formation of enone 2n , which was previously reported as a potential by‐product of the oxidation of 1q , was not observed 22. A sterically more demanding adamantyltrifluoromethylmethanol ( 1r ) also produced the corresponding ketone in high yield (entry 18, Table 2).…”

Section: Optimization Of the Reaction Conditions For The Catalytic Aementioning

confidence: 75%

A Tailored Catalyst for the Sustainable Conversion of Glycerol to Acrolein: Mechanistic Aspect of Sequential Dehydration

et al. 2014

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Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. An open-macropore-structured and Brønsted-acidic catalyst (Marigold-like silica functionalized with sulfonic acid groups, MS-FS) was synthesized for the stable and selective production of acrolein from glycerol. A high acrolein yield of 73% was achieved and maintained for 50 h in the presence of the MS-FS catalyst. The hierarchical structure of the catalyst with macropores was found to have an important effect on the stability of the catalyst because coke polymerization and pore blocking caused by coke deposition were inhibited. In addition, the behavior of 3-hydroxypropionaldehyde (3-HPA) during the sequential dehydration was studied using density functional theory (DFT) calculations because 3-HPA conversion is one of the main causes for coke formation. We found that the easily reproducible Brønsted acid sites in MS-FS permit the selective and stable production of acrolein. This is because the reactive intermediate (3-HPA) is readily adsorbed on the regenerated acid sites, which is essential for the selective production of acrolein during the sequential dehydration. The regeneration ability of the acid sites is related not only to the selective production of acrolein but also to the retardation of catalyst deactivation by suppressing the formation of coke precursors originating from 3-HPA degradation.

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Section: Optimization Of the Reaction Conditions For The Catalytic Aementioning

confidence: 75%

A Tailored Catalyst for the Sustainable Conversion of Glycerol to Acrolein: Mechanistic Aspect of Sequential Dehydration

et al. 2014

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“…In 2013, Leadbeater et al reported a Bobbitt's salt-mediated dehydrogenation of perfluoroalkyl ketones via the α-aminooxygenation of perfluoroalkyl ketones. 164 In 2017, Han et al…”

Section: Scheme 17 C-h Oxidation and C-o Cleavage Of Ethersmentioning

confidence: 99%

The Utility of Oxoammonium Species in Organic Synthesis: Beyond Alcohol Oxidation

Iwabuchi¹,

Nagasawa²

2022

HETEROCYCLES

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Oxoammonium species are electrophilic chemical species generated via single electron oxidation of nitroxyl radicals. Although this species and its salts are known as useful oxidants and active species for (catalytic) oxidation of alcohols into carbonyl compounds in organic synthesis, the benefits of oxoammonium species for the oxidative transformations of numerous types of substrates apart from alcohols has been reported. This review summarizes the synthetic utility of oxoammonium species under both stoichiometric and catalytic conditions with the exception of alcohol oxidation. CONTENTS 1. Introduction 2. Oxoammonium species 3. Oxoammonium species (salt)-mediated oxidative transformation 3-1. Oxidative esterification/amidation 3-2. Oxidation of amines (imines) 3-3. Oxidation of ethers 3-4. Oxidation of enols: α-Aminooxygenation of carbonyl compounds and further applications 3-5. Oxidation of alkenes 3-6. Oxidation of aromatic compounds 3-7. Oxidation of other substrates 3-8. Oxoammonium species for single electron oxidation 3-9. Oxoammonium species as a Lewis acids Conclusions and outlookThis paper is dedicated to Prof. Somsak Ruchirawat on the occasion of his 80th birthday.

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“…A great potential of these ketones was shown for the synthesis of various organofluorine compounds, including carbo- and heterocycles . Various approaches to the synthesis of α,β-unsaturated CF 3 -ketones can be found in the literature. − However, to the best of our knowledge, only a couple of works reported synthesis of α,β-diaryl-CF 3 -enones . Only four ketones of this class have been described.…”

Section: Introductionmentioning

confidence: 99%

α,β-Disubstituted CF₃-Enones as a Trifluoromethyl Building Block: Regioselective Preparation of Totally Substituted 3-CF₃-Pyrazoles

et al. 2021

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An efficient pathway toward a novel class of trifluoromethyl building blocks was elaborated. The reaction of α-CF3-enamines with arylaldehydes resulted in direct synthesis of α,β-diaryl-CF3-enones isolated in up to 93% yield as E-isomers. The possible reaction mechanism was proposed using the Zimmerman–Traxler model. The reaction of α,β-diaryl-CF3-enones with hydrazines opens a novel pathway to trifluoromethylated pyrazolines. Oxidation of pyrazolines with DDQ opened access to totally regioselective preparation of 3-CF3-pyrazoles isolated in high yield. Using this strategy, 4-arylated derivatives of known drugs Celebrex, Mavacoxib, and SC-560 can be synthesized.

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Dehydrogenation of Perfluoroalkyl Ketones by Using a Recyclable Oxoammonium Salt

Cited by 32 publications

References 58 publications

A Tailored Catalyst for the Sustainable Conversion of Glycerol to Acrolein: Mechanistic Aspect of Sequential Dehydration

A Tailored Catalyst for the Sustainable Conversion of Glycerol to Acrolein: Mechanistic Aspect of Sequential Dehydration

The Utility of Oxoammonium Species in Organic Synthesis: Beyond Alcohol Oxidation

α,β-Disubstituted CF₃-Enones as a Trifluoromethyl Building Block: Regioselective Preparation of Totally Substituted 3-CF₃-Pyrazoles

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Dehydrogenation of Perfluoroalkyl Ket­ones by Using a Recyclable Oxoammonium Salt

Cited by 32 publications

References 58 publications

A Tailored Catalyst for the Sustainable Conversion of Glycerol to Acrolein: Mechanistic Aspect of Sequential Dehydration

A Tailored Catalyst for the Sustainable Conversion of Glycerol to Acrolein: Mechanistic Aspect of Sequential Dehydration

The Utility of Oxoammonium Species in Organic Synthesis: Beyond Alcohol Oxidation

α,β-Disubstituted CF3-Enones as a Trifluoromethyl Building Block: Regioselective Preparation of Totally Substituted 3-CF3-Pyrazoles

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Product

Resources

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Dehydrogenation of Perfluoroalkyl Ketones by Using a Recyclable Oxoammonium Salt

α,β-Disubstituted CF₃-Enones as a Trifluoromethyl Building Block: Regioselective Preparation of Totally Substituted 3-CF₃-Pyrazoles