L-Piperidine-2-carboxylic acid

L-piperidine-2-carboxylic acid is a non-proteinogenic amino acid that is a metabolite of lysine. The zinc complexes of DL-piperidine-2-carboxylic acid, DL-piperidine-3-carboxylic acid, and piperidine-4-carboxylic acid have been studied. The X-ray crystal structures have been determined for the latter two. [ZnCl2(DL-piperidine 3-carboxylate)2] (42) is monomeric with a tetrahedral metal center and monodentate carboxylates. [Zn2Cl4(piperidine-4-carboxylate)2] (43) contains two bridging carboxylates in a dimeric structure. IR studies suggest that the DL-piperidine-2-carboxy-lato zinc has monodentate carboxylate ligands coordinating.392... 

Ruthenium(ll)-catalysed reactions of diamines or amino-alcohols have been used to prepare piperidines. A simple synthesis of L-piperidine-2-carboxylic acid (48) from L-lysine (47) has also been reported (Scheme 28). ... 

METHYLPIPERIDINE pOT) see MOG500 (l-METHYL-dl-PIPERIDINE-2-CARBOXYLIC ACID)-2,6-DIMETHYLANILIDE HYDROCHLORIDE see CBR250... 

Ornstein, P.L., Schoepp, D.D., Arnold, M.B., Leander, J.D., Lodge, D., Paschal, J.W., and Elzey, T., 4-(TetrazolylaIkyl)piperidine-2-carboxylic acids. Potent and selective JV-methyl-D-aspartic acid receptor antagonists with a short duration of action, J. Med. Chem., 34, 90, 1991. 

A stoichiometric amount (0.1 mM) each of enzyme-bound FAD and C-u-L-lysine (u = uniformly labelled) was incubated anaerobically until FAD was fully reduced. After deproteinization the reaction mixture was subjected to high voltage paper electrophoresis and paper chromatography. Most of the radioactivity appeared at the area corresponding to piperidine 2-carboxylic acid (a-keto-c-aminocaproic acid) (Figure 7), and a significant amount of carbon dioxide was not detected. When the reaction mixture was aerated to reoxidize FAD and then deproteinized, the radioactivity was also found at the position of piperidine 2-carboxylic acid. 

The potential of biotransformations with genetically modified microorganisms can be illustrated by the following example, where the chain of added-value to amino acid products is also recognisable The Mercian Company (Japan) uses a recombinant E. coli strain to prepare (S)-piperidine-2-car-boxylic acid from (L)-lysine. In this strain, the (L)-lysine-permease transport system is overexpressed, so that in this pathway lysine is produced efficiently in the cells. The bacteria possess additionally a (L)-lysine-aminotransferase from Flavobacterium lutescens, which brings about the deamination of lysine. The thus generated aldehyde is in equilibrium with its intramolecular imine, which, in presence of the E. co/i-specific pyrroline-5-carboxylate reductase, is reduced with NADPH to (S)-piperidine-2-carboxylic acid. The turnover... 

L-PIpecolic acid piperidine-2-carboxylic acid, a nonproteogenic amino acid. It is formed from L-ly-sine, either by a-deamination followed by cyclization and reduction, or as a normal intermediate in the degradation of lysine to a-aminoadipic acid. The 4- and 5-hydroxy derivatives of L-P.a. are found especially in mimosas and palms. 

Another interesting pathway to defense metabolites is illustrated by escapin in the defensive secretion of the sea hare Aplysia califomica. Escapin is an L-amino acid oxidase which oxidizes L-lysine in an equilibrium mixture of antipredatory and antimicrobial metabolites which depends on the pH. This enzymatic oxidation led to A -piperidine-2-carboxylic acid and H2O2 as the major components of the mixture. Then, a nonenzymatic reaction occurs between H2O2 and the former metabolites resulting in two end products, 8-aminovaleric add and 8-valer-olactam (Kamio et al., 2009). 

C8H15NO2 l-methyl-piperidine-2-carboxylic acid methyl ester 1690-74-0 ... 

L-Pipecolic acid, a key component of many antibiotic and anticancer biomolecules, serves as an important chiral pharmaceutical intermediate. We have developed an enzyme-coupled system consisting of zl -piperidine-2-carboxylate reductase (Pip2C) from Pseudomonas putida, glucose dehydrogenase (GDH) from Bacillus subtilis, and L-lysine a-oxidase from Trichoderma viride, affording L-pipecolic acid from L-lysine in high yield with an excellent enantioselectivity (Figure 10.2). ... 

Muramatsu, H., Mihara, H., Yasuda, M., Ueda, M., Kurihara, T. and Esaki, N., Enzymatic synthesis of L-pipecolic acid by d -piperidine-2-carboxylate reductase from Pseudomonas putida. Biosci. Biotechnol. Biochem., 2006, 70, 2296. 

For a,a-dialkylamino acids enantiomerization is not a problem. The preparation of 4,4-dimethyl-2-[(9-fluorenylmethyl)oxy]-5(4F/)-oxazolone, an intermediate used in the synthesis of ( )-mirabazole C has been described. Recently, two new 2-aIkoxy-5(4F/)-oxazolones derived from Toac (2,2,6,6-tetramethyl-4-amino-l-oxy-piperidine-4-carboxylic acid) that incorporate Z or 9-fluorenylmethoxycarbonyl (Fmoc) protection at C-2 have been described. The Toac analogues were synthesized as part of a study of the crystal structure and ab initio calculations for these interesting systems. 

The esterification of l-benzyM-(phenylamino) piperidine-4-carboxylic acid with ethanol and H2SO4 gives the corresponding ethyl ester, which is reduced with LiAIH2(0CH2CH20CH3)2 in benzene affording 1-benzyl-4-(phenylamino)piperidine-4-methanol. The methylation of this compound with methyl iodide and NaH in HMPA yields 1 -benzyl-4-methoxymethyl-4-(phenylamino)-... 

After studies of the structure and stereochemistry of betanidine and isobetanidine (ref. 36) the former was synthesised (ref.37). The indole component, the methyl ester of L-cyclodopa, 5,6-dihydroxyindoline-2-carboxylic acid, has been prepared (ref. 38) and the piperidine moiety, betalamic acid (ref.39) has been synthesised by another distinct route. 

An alternative strategy for the introduction of spin labels can be used in protein and peptide chemistry by spin label building blocks, e.g., 4-amino-l-oxyl-2,2,6,6-tetramethyl-piperidine-4-carboxylic acid (TOAC, Fig. 1, right) which are directly incorporated into the peptide during chemical synthesis [20-25]. 

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