Oxidative deamination of amino acids by molecular oxygen with pyridoxal derivatives and metal ions as catalysts

Shanbhag, Venkatesh M.; Martell, Arthur E.

doi:10.1021/ja00017a019

Cited by 15 publications

(6 citation statements)

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“…1109 Two reasonable mechanisms (Scheme 563 and Scheme 564) were in line with the experimental data obtained from 18 O 2 labeling, kinetic, and spectroscopic studies from the four previously proposed mechanisms described. Additionally, the authors were able to demonstrate the facile conversion of Cu(II) complex of the Schiff base to the oxime of the coenzyme.…”

Section: Reactions Of Aminessupporting

confidence: 84%

“…Only select cases describing the use of small molecule copper catalysts for oxidative deamination of amines have been described below. 1109,1110,1111 …”

Section: Reactions Of Aminesmentioning

confidence: 99%

“…A survey of the literature reveals that the substrate scope of small molecule copper catalysts mimicking the reactivity of copper-containing amine oxidase (CuAO) enzymes is limited. Only select cases describing the use of small molecule copper catalysts for oxidative deamination of amines have been described here. − …”

Section: Reactions Of Aminesmentioning

confidence: 99%

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Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

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24 peroxide [Cu I (pyr)(tpb)] 10 mol % TBHP, 1 atm O 2 , 1:2 AcOH/pyr, rt, 24 h ∼2.5 26 74 g 35 25 n-hexane aldehyde CuCl 2 , 18-crown-6 1 atm O 2 , MeCHO, CH 2 Cl 2 , 70 °C, 24 h 2.4 91 h 9 34a 26 n-decane aldehyde Cu II Cl 16 Pc-AM(PS) 3 equiv of PhCHO, MeCN, 1 atm O 2 , 50 °C 15.4 100 i 61 a See Chart 2 for ligand structures. b Also 28% cyclohexene. c Also 26% cyclohexene. d Mixture of alcohol and hydroperoxide. e Remainder of product is cyclohexene. f Approximately 93:7 of 1-adamantol/2-adamantol. g Approximately 98:2 of 1-adamantol/2-adamantol. h Afforded oxidation products in an approximately 1:1 ratio at the 2-and 3-positions. i Mixture of decanones.

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Section: Reactions Of Aminessupporting

confidence: 84%

“…Only select cases describing the use of small molecule copper catalysts for oxidative deamination of amines have been described below. 1109,1110,1111 …”

Section: Reactions Of Aminesmentioning

confidence: 99%

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Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

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“…More recently, a biomimetic oxidative deamination of benzylic amines was reported, which employs an ortho -naphthoquinone as the catalyst under aerobic conditions . Compared to the enzymatic processes, traditional synthetic methods for the oxidative deamination of linear primary amines usually suffer from poor selectivity, affording a mixture of aldehydes, imines, and carboxylic acids (Scheme b). , Until now, all reported methods required the use of sacrificial oxidants, which can be problematic in being intolerant toward other oxidizable functionalities and generating waste. − …”

Section: Introductionmentioning

confidence: 99%

Catalytic Oxidative Deamination by Water with H₂ Liberation

et al. 2020

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Selective oxidative deamination has long been considered to be an important but challenging transformation, although it is a common critical process in the metabolism of bioactive amino compounds. Most of the synthetic methods developed so far rely on the use of stoichiometric amounts of strong and toxic oxidants. Here we present a green and efficient method for oxidative deamination, using water as the oxidant, catalyzed by a ruthenium pincer complex. This unprecedented reaction protocol liberates hydrogen gas and avoids the use of sacrificial oxidants. A wide variety of primary amines are selectively transformed to carboxylates or ketones in good to high yields. It is noteworthy that mechanistic experiments and DFT calculations indicate that in addition to serving as the oxidant, water also plays an important role in assisting the hydrogen liberation steps involved in amine dehydrogenation.

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“…reactive molecular Cu(III)oxides, 7f,8 Cu(II)peroxides 9 Cu(II)hydroperoxides 10 and Cu(II)superoxides 4b,7e are proposed as intermediates in irreversible dehydrogenations, 11 benzylic 7e,9a,12 aromatic, 13 and aliphatic 14 C-H oxygenations, 15 alcohol oxidation 16 and oxidative deaminations. 17 The generation of reactive oxygen species (ROS) promoted by copper(II)-phenanthroline complexes is responsible for their ability to oxidatively cleave DNA; • OH and H 2 O 2 were the main ROS produced. 18 Our recent investigations of the coordination chemistry of a new tridentate ligand 1,2-di( pyridin-2-yl)ethanone oxime (dpeo) reveals that its aliphatic C-H groups can be selectively oxidized by oxygen from air in the presence of Mn(II), and that this reaction is catalytic.…”

Section: Introductionmentioning

confidence: 99%

Copper-promoted methylene C–H oxidation to a ketone derivative by O₂

2017

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The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O in air under ambient conditions when [Cu(dpeo)](ClO) is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca are not recovered and [Cu(pic)HO] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by HO in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O. The metastable copper complexes [Cu(dpeo)](ClO) and [Cu(bpca)(hidpe)](ClO), along with [NiX(dpeo)] (X = Cl, Br), [Ni(dpeo)](ClO), [Co(dpeo)](ClO) and the mixed valence complex [FeFe(dpeo-H)(dpeo)](PF), have been structurally characterized.

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Oxidative deamination of amino acids by molecular oxygen with pyridoxal derivatives and metal ions as catalysts

Cited by 15 publications

References 0 publications

Aerobic Copper-Catalyzed Organic Reactions

Aerobic Copper-Catalyzed Organic Reactions

Catalytic Oxidative Deamination by Water with H₂ Liberation

Copper-promoted methylene C–H oxidation to a ketone derivative by O₂

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Oxidative deamination of amino acids by molecular oxygen with pyridoxal derivatives and metal ions as catalysts

Cited by 15 publications

References 0 publications

Aerobic Copper-Catalyzed Organic Reactions

Aerobic Copper-Catalyzed Organic Reactions

Catalytic Oxidative Deamination by Water with H2 Liberation

Copper-promoted methylene C–H oxidation to a ketone derivative by O2

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Catalytic Oxidative Deamination by Water with H₂ Liberation

Copper-promoted methylene C–H oxidation to a ketone derivative by O₂