Additions and Corrections: A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide.

Anderson, Arthur G.; Berkelhammer, Gerald

doi:10.1021/ja01557a633

Cited by 11 publications

(16 citation statements)

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“…In accordance with the enamine (R-CH=CH-N<) structure of the dihydropyridine, its acid degradation most probably involves an initial P-protonation (Anderson and Berkelhammer, 1958).…”

Section: Discussionmentioning

confidence: 84%

“…Changes of the ultraviolet absorption spectrum of NADH in the presence of acid were first described by Haas (1936). The mechanism of this acid degradation was studied in detail with model dihydropyridine derivatives (Wallenfels et al, 1959;Anderson and Berkelhammer, 1958;Stock et al, 1961), and it was discussed by Kosower (1962, p. 166).…”

Section: Discussionmentioning

confidence: 99%

“…In acidic watery milieu, this initial protonation occurs very rapidly (Anderson and Berkelhammer, 1958;Stock et al, 1961 ;Burton and Kaplan, 1963). However, when the hydrogen ion concentration is very low (approximately pH 7.0), the over-all reaction rate from A (corresponding to NADH) to B (partly corresponding to the "primary acid product" of NADH) (see below) is too slow to be measured with accuracy (see Results, and Stock et af., 1961).…”

mentioning

confidence: 99%

“…This step would involve the reaction of an intermediate carbonium ion [i.e., compound 121 with a nucleophilic species. The above-mentioned nucleophilic substitution could perhaps be rate limiting in the presence of high hydrogen ion concentrations6 (Anderson and Berkelhammer, 1958), but, at pH 6.0 or above, the arguments mentioned above are against such a hypothesis.…”

mentioning

confidence: 99%

“…However, our recent studies on the structure of B failed again to demonstrate phosphate or other anions (with the exception of sulfite, see footnote 5 ) as a part of this structure, and this is in agreement with previous investigations Stock et al, 1961). Working at considerably higher hydrogen ion concentrations, Anderson and Berkelhammer isolated from l-benzyl-3-acetyl-1 &dihydropyridine a product with a hydroxyl at the 6 position (21), and they interpreted their results as due to solvent attack on the intermediate carbonium ion (12) (Anderson and Berkelhammer, 1958). There is no reason to postulate a different (from the above) course in spontaneous reactions of 1,3-substituted 1,4dihydropyridines with orthophosphates, etc., at low H+ concentrations.…”

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confidence: 99%

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Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates^*

Alivisatos¹,

Ungar²,

Abraham³

1965

Biochemistry

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The spontaneous reactions of reduced nicotinamide-adenine dinucleotide (NADH, DPNH) with orthophosphates in neutral watery milieu were analyzed kinetically. They can be described by three consecutive second-order (pseudo-first-order) reactions. A graphical procedure, suitable for this kinetic analysis, was based on the observation that kl >> k2 >> k?. With the aid of this kinetic analysis it was shown that the reaction most probably involves three consecutive direct transfers of protons from the polybasic anions, which in this case act as proton donors, to the 1,3-substituted 1 ,4-dihydropyridine. Proton transfer W e previously reported changes in the ultraviolet absorption spectra of nicotinamide-adenine dinucleotide (NAD)' in the presence of orthophosphates and certain other anions (Ungar and Alivisatos, 1961). In an extension of our observations, we recently studied the spontaneous reactions of NADH with dihydrogen phosphate and other "polybasic anions" (Stock et al., 1961;Alivisatos et a!., 1964b). The products of these primary interactions react further with the acid anions, in a series of consecutive second-order reactions. A detailed kinetic analysis of these processes, involving graphical evaluation of spectrophotometric data, became necessary. A description of this graphical analysis

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“…In accordance with the enamine (R-CH=CH-N<) structure of the dihydropyridine, its acid degradation most probably involves an initial P-protonation (Anderson and Berkelhammer, 1958).…”

Section: Discussionmentioning

confidence: 84%

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates^*

Alivisatos¹,

Ungar²,

Abraham³

1965

Biochemistry

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Stability of the 1,3-substituted 1,4-dihydropyridines: Substituent effects on the acid catalyzed hydration and oxidation reactions

Pop

Huang

Brewster

et al. 1994

Int. J. Quantum Chem.

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1,3-Substituted-1,4-dihydropyridines easily add water to the 5,6-double bond in acid catalysis resulting in 6-hydroxy-1,4,5,6-tetrahydropyriidines. The influence of various substituents in position C-5 and C-6 over the hydration of 1 -methyl-l,4-dihydromethylnicotinate, used as a model compound, was investigated in the framework of the AM 1 molecular orbital approximation. Since the rate-limiting step of the reaction is a proton transfer from the acidic species to the C-5 position of the substrate, calculated proton affinities (PA) were used as reactivity indexes. The results, in agreement with experimental evidences, indicated that electron-donating ( + I ) substituents increase the PA and destabilize I ,4-dihydropyridines towards hydration, while electron-withdrawing (-I) groups have the opposite effect. Calculated vertical ionization potentials (Ip) indicate that similarly + I groups facilitate the one-electron oxidation, while -I groups stabilize the molecules toward this reaction. Several molecular properties derived from the principle of maximum hardness were also used for the investigation of the stability of the dihydropyridines.

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Supported Pt Enabled Proton-Driven NAD(P)⁺ Regeneration for Biocatalytic Oxidation

Burnett

Chen

et al. 2022

ACS Appl. Mater. Interfaces

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The utilization of biocatalytic oxidations has evolved from the niche applications of the early 21st century to a widely recognized tool for general chemical synthesis. One of the major drawbacks that hinders commercialization is the dependence on expensive nicotinamide adenine dinucleotide (NAD(P)+) cofactors, and so, their regeneration is essential. Here, we report the design of carbon-supported Pt catalysts that can regenerate NAD(P)+ by proton-driven NAD(P)H oxidation with concurrent hydrogen formation. The carbon support was modified to tune the electronic nature of the Pt nanoparticles, and it was found that the best catalyst for NAD(P)+ regeneration (TOF = 581 h–1) was electron-rich Pt on carbon. Finally, the heterogeneous Pt catalyst was applied in the biocatalytic oxidation of a variety of alcohols catalyzed by different alcohol dehydrogenases. The Pt catalyst exhibited good compatibility with the biocatalytic system. Its NAD(P)+ regeneration function successfully supported biocatalytic conversion from alcohols to corresponding ketone or lactone products. This work provides a promising strategy for chemical synthesis via NAD(P)+-dependent pathways utilizing a cooperative inorganic-enzymatic catalytic system.

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Additions and Corrections: A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide.

Cited by 11 publications

References 0 publications

Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates^*

Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates^*

Stability of the 1,3-substituted 1,4-dihydropyridines: Substituent effects on the acid catalyzed hydration and oxidation reactions

Supported Pt Enabled Proton-Driven NAD(P)⁺ Regeneration for Biocatalytic Oxidation

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Additions and Corrections: A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide.

Cited by 11 publications

References 0 publications

Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates*

Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates*

Stability of the 1,3-substituted 1,4-dihydropyridines: Substituent effects on the acid catalyzed hydration and oxidation reactions

Supported Pt Enabled Proton-Driven NAD(P)+ Regeneration for Biocatalytic Oxidation

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Product

Resources

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Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates^*

Spontaneous Reactions of 1,3-Substituted 1,4-Dihydropyridines with Acids in Water at Neutrality. I. Kinetic Analysis and Mechanism of the Reactions of Dihydronicotinamide-Adenine Dinucleotide with Orthophosphates^*

Supported Pt Enabled Proton-Driven NAD(P)⁺ Regeneration for Biocatalytic Oxidation