The Preparation and Chemical Properties of Thionamides.

Hurd, Richard N.; DeLaMater, George

doi:10.1021/cr60209a003

Cited by 207 publications

(43 citation statements)

References 135 publications

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“…The conversion of sNAD+ as well as sNADH to cnNAD+ and its reduced form can be easily carried out by treatment with silver nitrate [15]. The sNADH is transformed into NADH by alkaline hydrogen peroxide [18,19]. All these reactions proceed in good yield if performed un-…”

Section: Discussionmentioning

confidence: 99%

Studies with Analogues of Nicotinamide Adenine Dinucleotide

Biellmann

Hirth

Jung

et al. 1974

European Journal of Biochemistry

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Through a series of correlative studies, the stereochemistry of the enzymatic processes with the coenzyme analogues of NAD+, 3-acetylpyridine-adenine dinucleotide, thionicotinamide-adenine dinucleotide and 3-cyanopyridine-adenine dinucleotide, have been examined for horse liver and yeast alcohol dehydrogenase (both A-specific for NAD+ ) and glutamate dehydrogenase (Bspecific for NAD+). I n each case the stereochemistry of the process with respect to substrate and coenzyme remains identical to that for NAD+. The implications for this are examined in view of the different geometry of the substituents a t the 3-position of the pyridine ring. A ready conversion of the thionicotinamide analogue of NADH to NADH is also described.Through the early pioneering work of Westheimer et al., the stereospecificity of the NAD+ or NADP+-dependent dehydrogenases for both the coenzyme and the substrate was demonstrated [1 to 31. I n particular it was shown that such enzymes could be classified into two distinct groups A and B depending on which side of the pyridinium ring, hydrogen transfer occurs [4,5]. I n a most elegant series of experiments by Cornforth et al., it was clearly demonstrated that the A-group enzymes abstracted the pro-R hydrogen a t C-4 of the dihydropyridine ring of NADH and the B-group enzymes the pro-S hydrogen [6,7].The stereochemistry of the hydrogen abstracted from C-1 of ethanol by the liver and the yeast alcohol dehydrogenases has been demonstrated as pro-R [8].A number of active analogues of NAD+ (NADP+) where the nicotinamide is replaced by a pyridine substituted a t C-3 with an electron-attracting group, for example thionicotinamide adenine dinucleotide (sNAD+) [9-111, selenonicotinamide adenine dinucleotide phosphate [ 121 and 3-acetylpyridine adenine dinucleotide (acNAD+) [13,14], have been prepared.However, as yet no study has been undertaken to determine whether such analogues posses the same Abbreviations. sNAD, thionicotinamide adenine dinucleotide; acNAD, 3-acetylpyridine adenine dinucleotide; cnNAD, 3-cyanopyridine adenine dinucleotide ; ORD, optical rotatory dispersion.Enzymes. NAD(P) nncleosidase (EC 3.2.2.6) ; alcohol dehydrogenase (EC 1.1.1.1) ; L-glutamate dehydrogenase (EC 1.4.1.2). stereochemical course as that for NAD+. Clearly is has been assumed that the similar geometry of the substituents a t C-3 of the pyridinium ring would result in an identical stereochemical reaction course. Recently we described the preparation of a new active analogue of NAD+, 3-cyanopyridine adenine dinucleotide (cnNAD+) [15]. Since this is the first analogue to be prepared with a linear functional group a t C-3 and since we have a t our disposal a ready means of correlation between sNADH and cnNADH by simple reaction with silver nitrate, we considered it informative to study the relative stereochemistry of the hydrogen transfer for these analogues. METHODS AND RESULTS MATERIALS AND GENERAL INDICATIONSNAD+ labeled grade 111, approx. 98O/, pure, pig's brain NAD( P) nucleosidase and the two dehydrogenases, hor...

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Section: Discussionmentioning

confidence: 99%

Studies with Analogues of Nicotinamide Adenine Dinucleotide

Biellmann

Hirth

Jung

et al. 1974

European Journal of Biochemistry

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“…The carbamoyl group and the amino group of the polymethylene chain are involved in a cooperative hydrogen-bonded system. A continuous characteristic IR absorption appears in the region 2870-1870 cm 1 . In a search for other parallels between structure and reactivity, the IR and NMR spectra of free base 10 were examined, where the intramolecular NÐ Ð ÐHN hydrogen bonds and additional dihydrogen interactions in the side-chain similar to 2a or 3 are absent.…”

Section: When Do Secondary Thioamides Not Cyclize To Cyclic Amidinesmentioning

confidence: 99%

“…1 The type of substituent and its position in the molecule relative to the thiocarbamoyl group influence the facility of either acidic or basic hydrolysis and the nature of the hydrolyzed products. Secondary thioamides were readily prepared by the transamination Wallach reaction.…”

Section: Introductionmentioning

confidence: 99%

Correlation between the reactivity and spectroscopic properties ofN‐substituted secondary thioamides. New intramolecular N···H⁺···N binding approach and proton complexes based on thioamide ligation

Spychala

2003

Magnetic Reson in Chemistry

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On the basis of a comparison of chemical shifts and wavenumbers of several secondary thioamides and amides having monocationic substituents attached to thiocarbamoyl or carbamoyl groups by a polymethylene chain, new intramolecular unconventional N· · ·H + · · ·N hydrogen bonding effects were discovered. It is argued that the CH 2 -N rotation is hindered and two + H· · ·NHCH 3 non-equivalent protons occur in a proton spectrum of hydrochloride 1a (at 10.68 and 2.77 ppm, respectively) instead of two + NH 2 CH 3 protons. Presumably, the above steric factors inhibit the acidic hydrolysis of 1a (stabilized by strong intramolecular N· · ·H + · · ·N hydrogen bonds) to an amide and prevent intramolecular cyclization of 2a (stabilized by strong intramolecular neutral-neutral N· · ·HN hydrogen bonds) to a cyclic amidine. Postulation of additional dihydrogen bond formation is helpful in understanding the spectroscopic differences of 4 and 5. The above new bonding is also compared with intramolecular N· · ·H -N + hydrogen bonds in primary amine salts 7 and 8. In contrast to 3, a cooperative hydrogen bonded system is observed in 9 and 10. The weak hydrogen bonds in 7-10 facilitate the hydrolysis and cyclization reactions of secondary thioamides. The spectroscopic data for secondary (thio)amides are especially useful for characterizing the electronic situation at the (thio)carbamoyl nitrogen atoms and they are perfectly correlated with the reactivity. Examples of chelation of protons by thioamides (11 and 12), which contain strongly electron-donating pyrimidine groups, are presented to show the contribution of dihydrogen bonding in the protonation reaction similar to 1 and 4.

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“…The only interference in the proposed method is the thiocarboxamide functional group. In Step 1 of the reaction sequence thioamides are converted to amidoximes (8) which results in the formation of the O-carboxamide derivative of a nonnitrile functional group.…”

Section: Recommended Proceduresmentioning

confidence: 99%

Determination of Isomeric Nitriles with High-Performance Liquid Chromatography after Separation by Derivatization

Pearse

Bovenzi

1997

Microchemical Journal

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The Preparation and Chemical Properties of Thionamides.

Cited by 207 publications

References 135 publications

Studies with Analogues of Nicotinamide Adenine Dinucleotide

Studies with Analogues of Nicotinamide Adenine Dinucleotide

Correlation between the reactivity and spectroscopic properties ofN‐substituted secondary thioamides. New intramolecular N···H⁺···N binding approach and proton complexes based on thioamide ligation

Determination of Isomeric Nitriles with High-Performance Liquid Chromatography after Separation by Derivatization

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The Preparation and Chemical Properties of Thionamides.

Cited by 207 publications

References 135 publications

Studies with Analogues of Nicotinamide Adenine Dinucleotide

Studies with Analogues of Nicotinamide Adenine Dinucleotide

Correlation between the reactivity and spectroscopic properties ofN‐substituted secondary thioamides. New intramolecular N···H+···N binding approach and proton complexes based on thioamide ligation

Determination of Isomeric Nitriles with High-Performance Liquid Chromatography after Separation by Derivatization

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Correlation between the reactivity and spectroscopic properties ofN‐substituted secondary thioamides. New intramolecular N···H⁺···N binding approach and proton complexes based on thioamide ligation