Über 1‐Cyan‐alkene‐(2) IV. Mitteilung über die Bildung von Nitrilen<sup>1.2.3)</sup>

Kurtz, Peter; Schwarz, Herbert; Disselnkötter, Hans

doi:10.1002/jlac.19606310104

Cited by 7 publications

(1 citation statement)

References 43 publications

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“…3-Chloro-3-butenenitrile was prepared from 2,3-dichloro-1-propene (Aldrich) and NaCN (Kurtz et al, 1960;Vessiére, 1959). The crude product was a 3:1 mixture of the nitrile and 3-chloro-3-buten-l-ol, which could not be cleanly separated by distillation: bp 35 °C (10 mm) for the fraction containing >95% nitrile (reported bp 39.5-40.5 °C (11 mm); Vessiére, 1959); NMR (CDC13) 5.55 (d, 1H,J= 1.5 Hz, cis H-C=C-Cl), 5.45 (d, 1 H, J = 2 Hz, trans H-C=C-Cl), and 3.4 (s, 2 H, C=CCH2CN).…”

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confidence: 99%

Mechanism of action of butyryl-CoA dehydrogenase: reactions with acetylenic, olefinic, and fluorinated substrate analogs

Fendrich¹,

Abeles²

1982

Biochemistry

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The acetylenic thio ester (3-pentynoyl)pantetheine irreversibly inactivates butyryl-CoA dehydrogenase from Megasphaera elsdenii. The inactivator becomes covalently attached to the protein (0.61 +/- 0.1 mol of 14C-labeled inactivator/mol of enzyme flavin). No modification of the flavin cofactor is seen. The covalent enzyme-inactivator adduct is labile toward base and neutral hydroxylamine. These treatments release 85 +/- 5% of the incorporated 14C label from the protein. Base-catalyzed hydrolysis of the adduct releases 3-oxopentanoic acid (0.6 mol/mol of incorporated inactivator). Treatment with hydroxylamine leads to formation of a hydroxamic acid on the protein (0.64 +/- 0.09 mol/mol of incorporated inactivator). The covalent adduct can be reduced with sodium borohydride with release of 1,3-pentanediol. Hydrolysis of the protein with 6 N HCl after sodium borohydride reduction yields 2-amino-5-hydroxyvaleric acid and proline. We conclude that the inactivator has reacted with the gamma-carboxyl group of a glutamate residue at the enzyme active site. The inactivation proceeds through enzyme-catalyzed rearrangement of the acetylene to an allene, followed by nucleophilic addition of the carboxyl group to the allene. (3-Chloro-3-butenoyl)pantetheine irreversibly inactivates the enzyme in a fashion similar to the acetylenic thio ester and also modifies a glutamate residue. Butyryl-CoA dehydrogenase catalyzes the isomerization of (3-butenoyl)pantetheine to (2-butenoyl)pantetheine. The enzyme catalyzes the elimination of HF from 3-fluoropropionyl-CoA and (3,3-difluorobutyryl)pantetheine. We suggest, that these results together support an oxidation mechanism for butyryl-CoA dehydrogenase which is initiated by alpha-proton abstraction.

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Mechanism of action of butyryl-CoA dehydrogenase: reactions with acetylenic, olefinic, and fluorinated substrate analogs

Fendrich¹,

Abeles²

1982

Biochemistry

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Introduction of the cyano group into the molecule

Friedrich

Wallenfels

1970

PATAI'S Chemistry of Functional Groups

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Chemie von α‐Aminonitrilen. 12. Mitteilung. Sondierungen über thermische Umwandlungen von α‐Aminonitrilen

Xiang

Drenkard

Baumann

et al. 1994

Helvetica Chimica Acta

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The paper extends a previously published report [4] on chemical properties of a -amino nitriles and of members of the C3H,N2 ensemble (Scheme I ) as observed in experiments carried out under non-aqueous conditions. The reactions investigated and the observations made are summarized in some detail in the English footnotes (*) referring to Schemes 1-17 and Fig. 1. Schenw 3 *) QCN H 18 CN QCN NC 19 H NC iN NHz HN flyN HzN 15 21 1 *) Retrosynthetic analysis of the structural relationship between the nitrile form of 1,4-dihydronicotinamide, and the glutamic and aspartic acid dinitriles. The relationship rests on the equivalence of glutamic acid dinitrile and acrolein imine under thermal conditions. *) Uber eine potentiell prabiotische Bildung von Asparaginsaure aus Cyanoacetylen mit HCN, NH3 in H,O vgl. Sanchez et ul. [lo]. 9, Eine Variante der Herstellung von 20 aus 22 und 4-Oxobutannitril ist in [4] beschrieben.Scheme 5 *) 2217 *) Hypothetical reaction paths to products in the FVP of (E/Z)-19 and 20. Within this framework of structural transformations, the nitrile form of 1,4-dihydronicotinamide is at the same oxidation level as the ensemble of the dinitrile forms of glutamic and aspartic acids. e-") Gestutzt wird diese Interpretation der Reaktionsmechanismen durch die Beobachtung, dass auch die hier nicht explizit beschriebene Pyrolyse des strukturvenvandten N-Propenylidenasparagindinitril (3-Azahexa-3,5-dien-1,2-dicarbonitril) zu den gleichen isolierbaren Produkten, ausschliesslich 26 und 27, fuhrt, wahrend die Pyrolyse von N-(I-Cyanoethy1iden)glutamindinitril (cl-Azahex-4-en-l,3,5-tricarbonitril) nur 26 und 29und 5-Methylpyrrol-2-carbonitril liefert (121, S . 62,68, 188, 199).

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Über 1‐Cyan‐alkene‐(2) IV. Mitteilung über die Bildung von Nitrilen^1.2.3)

Cited by 7 publications

References 43 publications

Mechanism of action of butyryl-CoA dehydrogenase: reactions with acetylenic, olefinic, and fluorinated substrate analogs

Mechanism of action of butyryl-CoA dehydrogenase: reactions with acetylenic, olefinic, and fluorinated substrate analogs

Introduction of the cyano group into the molecule

Chemie von α‐Aminonitrilen. 12. Mitteilung. Sondierungen über thermische Umwandlungen von α‐Aminonitrilen

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Über 1‐Cyan‐alkene‐(2) IV. Mitteilung über die Bildung von Nitrilen1.2.3)

Cited by 7 publications

References 43 publications

Mechanism of action of butyryl-CoA dehydrogenase: reactions with acetylenic, olefinic, and fluorinated substrate analogs

Mechanism of action of butyryl-CoA dehydrogenase: reactions with acetylenic, olefinic, and fluorinated substrate analogs

Introduction of the cyano group into the molecule

Chemie von α‐Aminonitrilen. 12. Mitteilung. Sondierungen über thermische Umwandlungen von α‐Aminonitrilen

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Über 1‐Cyan‐alkene‐(2) IV. Mitteilung über die Bildung von Nitrilen^1.2.3)