A Metal-Free General Procedure for Oxidation of Secondary Amines to Nitrones

Gella, Carolina; Ferrer, Èric; Alibés, Ramón; Busquè, Félix; March, Pedro de; Figueredo, Marta; Font, Josep

doi:10.1021/jo901108u

Cited by 87 publications

(43 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5 and 6 indicates the major amine degradation products observed by LCMS. Both alcohols will oxidize to form the respective amine oxides (N-oxides) or aminium radical cations [28,29,35–37]. The tetra-ol (HPED, starting material 7 ) will have steps analogous to the triol TEA to form N-oxide(s) or radical cation(s) (product 8 ), prior to any fragmentation occurring.…”

Section: Resultsmentioning

confidence: 99%

Shape memory polyurethanes with oxidation-induced degradation: In vivo and in vitro correlations for endovascular material applications

et al. 2017

View full text Add to dashboard Cite

The synthesis of thermoset shape memory polymer (SMP) polyurethanes from symmetric, aliphatic alcohols and diisocyanates has previously demonstrated excellent biocompatibility in short term in vitro and in vivo studies, although long term stability has not been investigated. Here we demonstrate that while rapid oxidation occurs in these thermoset SMPs, facilitated by the incorporation of multi-functional, branching amino groups, byproduct analysis does not indicate toxicological concern for these materials. Through complex multi-step chemical reactions, chain scission begins from the amines in the monomeric repeat units, and results, ultimately, in the formation of carboxylic acids, secondary and primary amines; the degradation rate and product concentrations were confirmed using liquid chromatography mass spectrometry, in model compound studies, yielding a previously unexamined degradation mechanism for these biomaterials. The rate of degradation is dependent on the hydrogen peroxide concentration, and comparison of explanted samples reveals a much slower rate in vivo compared to the widely accepted literature in vitro real-time equivalent of 3% H2O2. Cytotoxicity studies of the material surface, and examination of the degradation product accumulations, indicate that degradation has negligible impact on cytotoxicity of these materials.

show abstract

Section: Resultsmentioning

confidence: 99%

Shape memory polyurethanes with oxidation-induced degradation: In vivo and in vitro correlations for endovascular material applications

et al. 2017

View full text Add to dashboard Cite

show abstract

“…oxidation peak in the pH range of 2.0-10.0 (Fig. S2), and their electrochemical oxidation took place in secondary amine of benzyl amino side chain (Scheme 2) according to the literature [47][48][49][50]. However, there was a difference in voltammetric behaviors due to the difference of pK a values (Table 1) resulted from the difference of their substituent groups (Scheme S2).…”

Section: Electrocatalytic Oxidation Mechanism Of 6-bapmentioning

confidence: 71%

pH-controlled voltammetric behaviors and detection of phytohormone 6-benzylaminopurine using MWCNT/GCE

Wen

Bai

et al. 2015

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

“…It has been well studied in the literature as an oxidant for the Shi epoxidation reactions; [11] cleavage of alkenes [12] and alkynes [13] to ketones and carboxylic acids; a-hydroxylation of aryl alkyl ketones; [14] and in the oxidation of tertiary amines to the corresponding nitrones. [15] However, the examples of Oxone-based protocols for the oxidation of alcohols are scarce.…”

Section: Resultsmentioning

confidence: 99%

Application and Mechanistic Studies of a Water‐Oxidation Catalyst in Alcohol Oxidation by Employing Oxygen‐Transfer Reagents

Verho

Dilenstam

Kärkäs

et al. 2012

Chemistry A European J

View full text Add to dashboard Cite

By using a dimeric ruthenium complex in combination with tert-butyl hydrogen peroxide (TBHP) as stoichiometric oxidant, a mild and efficient protocol for the oxidation of secondary benzylic alcohols was obtained, thereby giving the corresponding ketones in high yields within 4 h. However, in the oxidation of aliphatic alcohols, the TBHP protocol suffered from low conversions owing to a competing Ru-catalyzed disproportionation of the oxidant. Gratifyingly, by switching to Oxone (2 KHSO(5)⋅KHSO(4)⋅K(2)SO(4) triple salt) as stoichiometric oxidant, a more efficient and robust system was obtained that allowed for the oxidation of a wide range of aliphatic and benzylic secondary alcohols, giving the corresponding ketones in excellent yields. The mechanism for these reactions is believed to involve a high-valent Ru(V)-oxo species. We provide support for such an intermediate by means of mechanistic studies.

show abstract

A Metal-Free General Procedure for Oxidation of Secondary Amines to Nitrones

Cited by 87 publications

References 11 publications

Shape memory polyurethanes with oxidation-induced degradation: In vivo and in vitro correlations for endovascular material applications

Shape memory polyurethanes with oxidation-induced degradation: In vivo and in vitro correlations for endovascular material applications

pH-controlled voltammetric behaviors and detection of phytohormone 6-benzylaminopurine using MWCNT/GCE

Application and Mechanistic Studies of a Water‐Oxidation Catalyst in Alcohol Oxidation by Employing Oxygen‐Transfer Reagents

Contact Info

Product

Resources

About