Protocols for the Catalytic Oxidation of Primary Amines to Imines

Largeron, Martine

doi:10.1002/ejoc.201300315

Cited by 152 publications

(80 citation statements)

References 84 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Further, transition metals such as those present in carbonaceous chondrites can potentially catalyze oxidation reactions through aqueous processes, transforming amines into more polar compounds inside the Orgueil parent body (Murahashi ; Soulé et al. ; Largeron ); therefore, finding higher amounts of methylamine in Orgueil relative to Murchison was an unexpected result.…”

Section: Resultsmentioning

confidence: 99%

“…; Glavin and Dworkin ), it might be expected that the concentration of amines surviving inside Orgueil would be low due to the potential catalytic effects of transition metals in the destruction of organics (Murahashi ; Soulé et al. ; Largeron ). We have recently developed an analytical method to study the abundance, molecular distribution, and δ 13 C isotopic composition of meteoritic amines and applied it to the Murchison meteorite (Aponte et al.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

Aponte

Dworkin

Elsila

2015

Meteorit & Planetary Scien

View full text Add to dashboard Cite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbonrich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound-specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g À1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent-body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound-specific stable carbon isotopic ratios (d 13 C) for 5 of the 12 monoamines detected in Orgueil and found a range of d 13 C values from -20 to +59&. These d 13 C values fall into the range of other meteoritic organic compounds, although they are 13 C-depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)-and (S)-sec-butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the L-enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec-butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of aqueous alteration observed over the monoamine concentrations in Orgueil and Murchison, and to evaluate the primordial synthetic relationships between meteoritic monoamines and amino acids.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

Aponte

Dworkin

Elsila

2015

Meteorit & Planetary Scien

View full text Add to dashboard Cite

show abstract

“…In 4 spite of good yields and selectivity, all of the catalysts either have cumbersome preparation methods or require the use of harsh reaction conditions such as high pressure, light irradiation, and use of oxidative promoters 20,26 . Moreover, limited activity of aliphatic amines with undesired side reactions is another flaw for the reported systems 27,28 . Despite good activity in the syntheses of symmetrical imines, syntheses of asymmetrically substituted imines by cross condensation of two amines have barely been discussed 29,30 .…”

Section: Introductionmentioning

confidence: 98%

Aerobic Oxidation of Amines to Imines by Cesium-Promoted Mesoporous Manganese Oxide

et al. 2015

View full text Add to dashboard Cite

Selective oxidation of amines to imines is one of the most studied reactions in the field of heterogeneous catalysis. Cs ion promoted mesoporous manganese oxide (meso Cs/MnO x ) was synthesized using inverse surfactant micelle as a soft template. The chemical and structural properties of the mesoporous manganese oxide material were characterized by powder X-ray diffraction (PXRD), nitrogen sorption, electron microscopy and X-ray photoelectron spectra (XPS). The meso-Cs/MnO x material presented aggregated nanocrystalline nature with monomodal mesoporous size distributions. The catalyst was found to be effective in oxidation of amines to imines under aerobic conditions. The meso Cs/MnO x exhibited oxidation of primary, secondary, cyclic, aromatic, and aliphatic amines to imines, where the conversions reached as high as >99%. The catalyst was also effective in oxidative cross condensation of two different amines to produce asymmetrically substituted imines. Surface active Mn 3+ species along with labile lattice oxygen were found to play an important role in the catalytic activity. Mild reaction conditions (air atmosphere and absence of any oxidative or basic promoters), ease of product separation by simple filtration and significant reusability make this mesoporous manganese oxide material an economical and ecofriendly catalyst for the syntheses of versatile imine derivatives.

show abstract

“…Thus, it varied from around 30 min for Au/Ce 60 -Ni 10 -UVM-7(200) and Au/Ce 30 -Ni 10 -UVM-7(200) up to 50 min for Au/Sn 30 -Ni 10 -UVM-7(500) and Au/Sn 10 -Ni 10 -UVM-7(500). The supplementary addition of 10 μL of water to the reaction system caused an increase in productivity from 4.04 ( 23,65 The produced benzaldehyde was suggested to react with excess benzylamine to form benzylidene benzylamines resulting in the final product for the benzylamine self-coupling reactions. To confirm this behavior we have carried out experiments on the same Au/Ce 60 -Ni 10 -UVM-7(200) and Au/Ce 30 -Ni 10 -UVM-7(200) catalysts by introducing benzaldehyde in the reaction mixture.…”

Section: View Article Onlinementioning

confidence: 98%

New multicomponent catalysts for the selective aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine

Opris

Pavel

Moragues

et al. 2014

Catal. Sci. Technol.

View full text Add to dashboard Cite

Aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine was carried out on new gold-based catalysts using as support bimodal UVM-7-like mesoporous silica containing Ni and Ce (or Sn) as oxide nanodomains partially embedded inside the mesoporous UVM-7 silica walls. These nanodomains acted as effective and stable inorganic anchors favoring the nucleation, growth and stability of supported gold particles. Following the atrane method (a "one-pot" strategy able to harmonize the hydrolytic reactivity of different heteroelements through the use of complexes containing triethanolamine-derived ligands (atranes) as precursors) the stability of the oxide nanodomains during oxidation and thermal treatments was ensured. The catalysts were prepared using a two-step synthesis in which gold was incorporated through impregnation of previously synthesized bimodal porous silicas containing different heteroelements trapped by the silica mesostructure. The versatility of the preparative approach allowed the high surface area and accessibility of mesoporous silica and also an easy and homogeneous inclusion of heteroelements in one pot. Aerobic oxidative condensation of benzylamine on these catalysts occurred selectively only with the formation of N-benzylidenebenzylamine. While selectivity was total, the productivities (mol product g cat −1 h −1 ) varied in a wide range as a function of catalyst composition (chemical composition and atomic ratios of the constitutive support elements). The catalytic behavior was merely controlled by the size of gold particles, but the support also exerts an influence. The best results were obtained on the mesoporous Au/Ce 60 -Ni 10 -UVM-7 catalyst having a 0.97(wt.%) gold content (in the form of nanoparticles of ca. 4 nm) and preserving a relatively high surface area (566 m 2 g −1 ) and pore volume (0.91 cm 3 g −1 ).The comparison with the individual or bicomponent catalysts led to the conclusion of a cooperative interaction between the catalyst components. However, gold itself exhibits a higher activity than the promoters or co-catalysts (i.e. phases containing Ni and/or Ce).

show abstract

Protocols for the Catalytic Oxidation of Primary Amines to Imines

Cited by 152 publications

References 84 publications

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

Aerobic Oxidation of Amines to Imines by Cesium-Promoted Mesoporous Manganese Oxide

New multicomponent catalysts for the selective aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine

Contact Info

Product

Resources

About