The NEF Reaction

Noland, Wayl­and E.

doi:10.1021/cr50001a003

Cited by 227 publications

(77 citation statements)

References 24 publications

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“…[1-2H]Propionaldehyde, b. p. 48 -52 "C, n' ," = 1.3637, was prepared from l-nitr0 [2,2-~H]propane by the Nef reaction [12]. Nuclear magnetic resonance and mass spectra were consistent with the assumed structure and showed virtually complete deuteration of the aldehydic hydrogen position.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of Sheep‐Liver Cytoplasmic Aldehyde Dehydrogenase

MacGibbon

Blackwell

Buckley

1977

European Journal of Biochemistry

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1. Sheep liver cytoplasmic aldehyde dehydrogenase showed little pH dependence of V or k,,,. Some buffer anion effects were noted.2. The oxidation of aldehydes at pH 7.6 was quantitative but irreversible. The initial velocity data indicated a sequential mechanism for the addition of substrates. Inhibition by NADH and the product analogue 2-bromo-2-phenylacetic acid, together with the known tight binding of NADH to the free enzyme, indicated an ordered mechanism with NAD+ as leading substrate.3 . Values for the rate of binding and dissociation of NAD+ were obtained from the steady-state data. The values obtained were virtually identical with those which could be calculated from the data for the horse liver cytoplasmic enzyme. Close similarities are in general apparent for the horse and sheep liver cytoplasmic enzymes and with other tissue aldehyde dehydrogenases.4. Apparent substrate activation was observed with high concentrations of both acetaldehyde and propionaldehyde, a limiting value of 0.25 spl being obtained for k,,,. No isotope effect was observed on V using [l-'Hlpropionaldehyde as substrate suggesting that NADH release might be rate-limiting in the steady-state.5. The implications of the non-linear steady-state behaviour are discussed.In recent years aldehyde dehydrogenases from various sources have been purified to homogeneity [1,2]. More recently the purification of sheep liver cytoplasmic and mitochondrial enzymes has been reported [3] and the two major isozymes of aldehyde dehydrogenase from horse liver, which also appear to be cytoplasmic and mitochondrial in origin, have been purified and characterised [4]. An enzyme from human liver has also been studied [ 5 ] and the kinetics of aldehyde oxidation investigated, although its cellular localization is unknown.All the kinetic investigations so far reported suggest sequential mechanisms but the order of substrate addition varies from one enzyme to another. Pig brain, horse liver and bovine liver enzymes have been reported to follow compulsory order mechanisms in which NAD+ binds before aldehyde [2,6-8], but evidence has also been presented for the yeast enzyme [9] which indicates an ordered mechanism in which aldehyde binds first.The human liver enzyme appears to be partially random in its addition of its substrates, although most of the reaction is considered to proceed by means of an initial binary NAD' . enzyme complex [5]. In view of the importance of these enzymes in an understanding of human alcohol metabolism we have undertaken a detailed kinetic study of sheep liver cytoplasmic aldehyde dehydrogenase in order to determine the steady-state parameters for the reaction. MATERIALS AND METHODS MaterialsNADH (grade 111) and NAD' (grade 111) were obtained from Sigma Chemical Co. (St Louis, Mo., U.S.A.). The NADH was obtained as preweighed vials and the concentration was checked by absorbance measurements at 340 nm assuming a molar absorption coefficient (8) of 6 . 2 2~ lo3 M-l cm-I [lo]. NADt was used without further purification since no detectable...

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Section: Methodsmentioning

confidence: 99%

Kinetics of Sheep‐Liver Cytoplasmic Aldehyde Dehydrogenase

MacGibbon

Blackwell

Buckley

1977

European Journal of Biochemistry

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“…Since its discovery at the endo ft he nineteenth century,t he Nef reactionh as been widely exploited for the generation of carbonyls ystems in simple and functionalized molecules. [2][3][4][5] Ther elationship which connects nitroalkanes and the corresponding carbonyl systems fairly resembles that existing between alcohols and their oxidized counterparts.A samatter of fact, primary nitroalkanes can be converted into aldehydeso rc arboxylic acids depending on the adopted reactionc onditions,w hiles econdary nitro compounds are transformedi nto ketones.T his reactionw as originally designed as the hydrolysiso fn itronic acids,g enerated from the corresponding nitronate anions under strongly acidic conditions.O ver the years the Nef reaction has progressively modified its nature being nowadays carriedo ut under different reactionc onditions.C leavage of the C=Ns ystem can be performed under oxidative conditions on nitronates 2 obtained from nitroalkanes 1 using basic promoters (Scheme 1). [6] Reducing reagents can also be applied directlyo nn itroalkanesa si nt he classicalM cMurry procedure using aqueous solutions of TiCl 3 .T his may resulti nt he formation of the oxime 3 or the carbonyl derivative 4.…”

Section: Introductionmentioning

confidence: 99%

The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation

2015

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This review article reports new procedures and practical application of the nitro to carbonyl conversion that appeared in the literature after our\ud comprehensive report published in 2004. Beside traditional and well explored reactant systems, new procedures including the utilization of molecular oxygen and photoredox catalysis have been introduced for the Nef reaction. Of notable interest is the utilizationof the nitro to carbonyl conversion in tandem and cascade processes aimed at the preparation of hetero and carbocyclic derivatives

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“…The decomposition of the nitro compound in aqueous media provides an oxidized organic product with a carbonyl group and the reduced nitrosyl anion, which spontaneously produces nitrous oxide (Noland, 1955;Hawthorne 1957;Pinnick 1990;March 1992). This reaction usually is carried out in acidic solution, hut there are many examples of the reaction in alkaline media (Pinnick 1990 The chemistry of the nitrosyl anion, which leads directly to nitrous oxide, is discussed in Section 4.3.…”

Section: -36 Rpp-6664 Revmentioning

confidence: 99%

The Chemistry of Flammable Gas Generation

Zach¹

2000

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The NEF Reaction

Cited by 227 publications

References 24 publications

Kinetics of Sheep‐Liver Cytoplasmic Aldehyde Dehydrogenase

Kinetics of Sheep‐Liver Cytoplasmic Aldehyde Dehydrogenase

The Nitro to Carbonyl Conversion (Nef Reaction): New Perspectives for a Classical Transformation

The Chemistry of Flammable Gas Generation

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