Zur Darstellung von Δ¹‐Pyrrolin‐carbonsäure‐(2) und eine neue Prolinsynthese

Abstract

Herrn Professor D r . F, Micheel zum 60. Geburtstag 2.3-Dioxo-piperidin-carbonsaure-(4)-athylester wird durch Oxalesterkondensation aus Pyrrolidon-(2) dargestellt und zu a-Keto-6-amino-valerianslurehydrochlorid (offene Form von A I-Pyrrolin-carbonsaure-(2)) hydrolysiert. Letztere Verbindung ist zu Prolin hydrierbar. u-Keto-8-amino-valerianslure (1) und die mit ihr in waRriger Losung im Gleichgewicht stehendc cyclische Form : A~-Pyrrolin-carbonsaure-(2) (11) sind Intermediarprodukte des Prolinstoffwechsels. I1 entsteht bei der enzyniatischen Oxydation des Prolins und ist moglicherweise eine Vorstufe der Biogenese des Prolins, denn sie lPBt sich enzymatisch rnit A. MEISTER~) hat I1 Hydrobromid erhalten DPNH zu L-Prolin reduzieren. I I 1 durch enzymatische Oxydation von N*-Carbobenzoxy-ornithin als SKURSKY und MACHOLAN 2) konnten das Hydrochlorid der wahrscheinlich offenkettigen Form I darstellen. Sie fuhrten y-Phthalimido-butterslure uber eine groRere Zahl von Zwischenstufen in 8-Phthalimido-a-keto-valeriansaure Uber, aus der das Hydrochlorid von I durch Hydrolyse gewonnen werden konnte.

Reversible reduction of an .alpha.-imino acid to an .alpha.-amino acid catalyzed by glutamate dehydrogenase: effect of ionizable functional groups

“…DL-Proline-2-</ purchased from Merck Sharp and Dohme was crystallized from ethanol and ethanol-ether. a-Keto-5-aminovaleric acid was synthesized as the hydrochloride salt by the method of Hasse & Wieland (1960). This compound when dissolved in water at pH >4 spontaneously cyclizes to PCA (Cabello et al, 1964; Macholan & Vencalkova, 1963).…”

“…The burst of reduced nicotinamide adenine dinucleotide phosphate (NADPH) disappearance observed by Jallon et al (1975) for the reductive amination of -ketoglutarate was interpreted to include both the imine formation and NADPH oxidation steps. Similarly, for the oxidative deamination of glutamate the burst phase (Iwatsubo & Pantaloni, 1967), which appears to include the hydride transfer event, may well contain contributions from the subsequent imine hydrolysis steps (Fisher et al, 1970;…”

Comparison of the energetics of the uncatalyzed and glutamate dehydrogenase catalyzed .alpha.-imino acid-.alpha.-amino acid interconversion

“…L-Proline from Sigma was purified by repeated crystallization from aqueous ethanol. a-Keto-S-aminovaleric acid was synthesized as the hydrochloride salt (Hasse & Wieland, 1960). This compound spontaneously cyclizes to PCA upon dissolution in water at pH >2 (Cabello et al, 1964;Macholan & Vencalkova, 1963).…”

Muscarinic Receptor Agonists and Antagonists

“…The first reported synthesis of 1-aza-norbornan-3-one ( 41a ) commences with the condensation of 2-pyrrolidinone ( 44 ) with diethyl oxalate ( 43 ) to give the diketoester ( 45 ). This reaction proceeds via N -acylation of 2,3-pyrrolidinone, ring opening of the imide and a Dieckmann cyclisation to give the diketoester ( 45 ) which exists predominantly as the enol ( 46 ) [ 82 ]. Catalytic hydrogenation gives the cis -hydroxy-ester which is reduced to the diol ( 48a ).…”