A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide<sup>1,2</sup>

Anderson, Arthur G.; Berkelhammer, Gerald

doi:10.1021/ja01537a063

Cited by 163 publications

(67 citation statements)

References 7 publications

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“…[38] Hantzsch 1,4-dihydropyridine was prepared by depositing the mixture of aldehyde, ammonia, and ethyl acetoacetate in methanol. N-Methylated Hantzsch 1,4-dihydropyridines were prepared according to the literature.…”

Section: Methodsmentioning

confidence: 99%

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Zhu

et al. 2003

Chemistry A European J

149

134

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Heterolytic and homolytic bond dissociation energies of the C4-H bonds in ten NADH models (seven 1,4-dihydronicotinamide derivatives, two Hantzsch 1,4-dihydropyridine derivatives, and 9,10-dihydroacridine) and their radical cations in acetonitrile were evaluated by titration calorimetry and electrochemistry, according to the four thermodynamic cycles constructed from the reactions of the NADH models with N,N,N',N'-tetramethyl-p-phenylenediamine radical cation perchlorate in acetonitrile (note: C9-H bond rather than C4-H bond for 9,10-dihydroacridine; however, unless specified, the C9-H bond will be described as a C4-H bond for convenience). The results show that the energetic scales of the heterolytic and homolytic bond dissociation energies of the C4-H bonds cover ranges of 64.2-81.1 and 67.9-73.7 kcal mol(-1) for the neutral NADH models, respectively, and the energetic scales of the heterolytic and homolytic bond dissociation energies of the (C4-H)(.+) bonds cover ranges of 4.1-9.7 and 31.4-43.5 kcal mol(-1) for the radical cations of the NADH models, respectively. Detailed comparison of the two sets of C4-H bond dissociation energies in 1-benzyl-1,4-dihydronicotinamide (BNAH), Hantzsch 1,4-dihydropyridine (HEH), and 9,10-dihydroacridine (AcrH(2)) (as the three most typical NADH models) shows that for BNAH and AcrH(2), the heterolytic C4-H bond dissociation energies are smaller (by 3.62 kcal mol(-1)) and larger (by 7.4 kcal mol(-1)), respectively, than the corresponding homolytic C4-H bond dissociation energy. However, for HEH, the heterolytic C4-H bond dissociation energy (69.3 kcal mol(-1)) is very close to the corresponding homolytic C4-H bond dissociation energy (69.4 kcal mol(-1)). These results suggests that the hydride is released more easily than the corresponding hydrogen atom from BNAH and vice versa for AcrH(2), and that there are two almost equal possibilities for the hydride and the hydrogen atom transfers from HEH. Examination of the two sets of the (C4-H)(.+) bond dissociation energies shows that the homolytic (C4-H)(.+) bond dissociation energies are much larger than the corresponding heterolytic (C4-H)(.+) bond dissociation energies for the ten NADH models by 23.3-34.4 kcal mol(-1); this suggests that if the hydride transfer from the NADH models is initiated by a one-electron transfer, the proton transfer should be more likely to take place than the corresponding hydrogen atom transfer in the second step. In addition, some elusive structural information about the reaction intermediates of the NADH models was obtained by using Hammett-type linear free-energy analysis.

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Section: Methodsmentioning

confidence: 99%

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Zhu

et al. 2003

Chemistry A European J

149

134

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“…However, this method has several disadvantages including longer reaction times, the us of an excess amount of organic solvent, lower product yields and harsh refluxing conditions. Since the method of Hantzsch was described more than a use century ago [17][18][19] , several efficient methods have been developed for the synthesis of 1, 4-dihydropyridines that involve the use of a microwave [20][21][22] , ionic liquids [23][24] , high temperatures in refluxing solvent [25][26][27][28][29][30][31][32][33][34][35] , TMSCl-NaI 36 and metal triflates 37 . However, the use of high temperatures, expensive metal precursors and the resultant longer reaction times limit these methods.…”

Section: Introductionmentioning

confidence: 99%

Al2(SO4)3 IS AN EFFICIENT AND MILD ACID CATALYST FOR THE ONE-POT, FOUR-COMPONENT SYNTHESIS OF POLYHYDROQUINOLINE

Kulkarni¹

2014

J. Chil. Chem. Soc.

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Aluminium sulfate has mild acidity, yet the acidity of aluminium sulfate is not taken advantage of in organic synthesis. Here, we utilized aluminium sulfate for the first time in a multicomponent reaction for the synthesis of polyhydroquinoline. A four-component one-pot synthesis of polyhydroquinoline was carried out by condensing dimedone, aromatic aldehyde, ethyl acetoacetate, and ammonium acetate using a catalytic amount of aluminium sulfate (10%) refluxed in ethanol. The present protocol using aluminium sulfate a mild solid catalyst has several merits, such as low cost, high yield, and shorter reaction time, with no byproducts.

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“…Since the presence of the large and sensitive nucleotide R group complicates the work, numerous investigations were carried out on model compounds where R has been replaced by smaller and more stable groups. Anderson & Berkelhammer (1958) carried out the primary acid modification on (II)(Bz=benzyl), obtaining a product which they identified as (III), further suggesting that also in the case of the amide the reaction would be an addition of H20 to the 5-6 double bond, with the OH group going to C(6). However, other authors questioned the validity of their conclusions on the grounds that replacement of NH2 by CH3 might have resulted in a compound which could no longer be considered an adequate model.…”

Section: Introductionmentioning

confidence: 99%

The crystal structure of 1-(2,6-dichlorobenzyl)-6-hydroxy-1,4,5,6-tetrahydronicotinamide dihydrate

Hope¹

1969

Acta Crystallogr Sect B

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A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide^1,2

Cited by 163 publications

References 7 publications

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Al2(SO4)3 IS AN EFFICIENT AND MILD ACID CATALYST FOR THE ONE-POT, FOUR-COMPONENT SYNTHESIS OF POLYHYDROQUINOLINE

The crystal structure of 1-(2,6-dichlorobenzyl)-6-hydroxy-1,4,5,6-tetrahydronicotinamide dihydrate

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A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide1,2

Cited by 163 publications

References 7 publications

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Al2(SO4)3 IS AN EFFICIENT AND MILD ACID CATALYST FOR THE ONE-POT, FOUR-COMPONENT SYNTHESIS OF POLYHYDROQUINOLINE

The crystal structure of 1-(2,6-dichlorobenzyl)-6-hydroxy-1,4,5,6-tetrahydronicotinamide dihydrate

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A Study of the Primary Acid Reaction on Model Compounds of Reduced Diphosphopyridine Nucleotide^1,2