Norvaline

Fig. 2-5. Examples showing the eomplementary separations on glyeopeptide CSPs. (A) Separation of N-CBZ-norvaline on vaneomyein (left) and teieoplanin (right). The mobile phase was methanol 1 % triethylammonium aeetate (20/80 v/v) pH 4.1. (B) Separation of warfarin on teieoplanin (left) and vaneomyein (right) CSPs. The mobile phase was aeetonitrile 1 % triethylammonium aeetate (10/90 v/v) pH 4.1. (C) Separation of naproxen on teieoplanin (left) and ristoeetin A (right). The mobile phase was methanol 0.1 % triethylammonium aeetate (30/70 v/v) pH 4.1. All eolumns were 250 x 4.6 mm i.d. The flow rate for all the separations was 1 mL min at ambient temperature (23 °C).

In a modification of the above method, isolated crude imines characterized by their IR spectra are reacted with a solution of hydrogen cyanide in absolute ethanol42. An example is the transformation of the butyraldimine 2 to the norvalinonitrile 3 which is hydrolyzed to the, V-(1 -phenylethyljamino acid 4, then hydrogenolyzed to give norvaline (5). 

S)-2-aminopentanoic acid (norvaline) (hydrochloride salt) yield 41% (overall) 99% op... 

Ethyl (bornylideneamino)acetate (2) and the imines of (-)-(lf ,2, 5 )-2-hydroxy-3-pinanone and glycine, alanine and norvaline methyl esters were particularly successful as Michael donors. The chiral azaallyl anions, derived from these imines by deprotonation with lithium diisopropylamide in THF at — 80 C, add to various a,/i-unsaturated esters with modest to high diastereoselectivity (see Section 1.5.2.4.2.2.5.). Thus, starting with the imine 2, (R1 = CH,) and ethyl ( )-2-butcnoate, the a,/i-dialkylated glutamate derivative 3 is obtained as a single diastercomer in 90% yield91-92. 

S.P. solid-phase technique L.P. liquid-phase technique OPTcp pentachlorophenyl ester TEEP tetraethyl pyrophosphit OTCp trichlorophenyl ester ONp p-nitrophenyl ester ONSu N-hydroxysuccinimido ester OPFp pentafluorophenyl ester OQu 8-hydroxyquinyl ester OPy 3-hydroxy-pyridyl ester ODnp 2,4-dinitrophenyl ester DCC dicyclohexylcarbodiimide HOBn 3-hydroxy-4-oxo-3,4-dihydro-l,2,3-benzotriazin Opi JV-hy-droxypiperidine EEDQ 2-ethoxy-l-ethoxycarbonyl-l,2-dihydroquinoline Tos p-toluenesulfonyl PTC propanetricarboxylic acid OBu tm-butyl ester Nva norvaline Aha aminohexanoic acid Om ornithine... 

An alternative to extraction crystallization is used to obtain a desired enantiomer after asymmetric hydrolysis by Evonik Industries. In such a way, L-amino acids for infusion solutions or as intermediates for pharmaceuticals are prepared [35,36]. For example, non-proteinogenic amino acids like L-norvaline or L-norleucine are possible products. The racemic A-acteyl-amino acid is converted by acylase 1 from Aspergillus oryzae to yield the enantiopure L-amino acid, acetic acid and the unconverted substrate (Figure 4.7). The product recovery is achieved by crystallization, benefiting from the low solubility of the product. The product mixture is filtrated by an ultrafiltration membrane and the unconverted acetyl-amino acid is reracemized in a subsequent step. The product yield is 80% and the enantiomeric excess 99.5%. 

The question of the stability of the biomolecules is a vital one. Could they really have survived the tremendous energies which would have been set free (in the form of shock waves and/or heat) on the impact of a meteorite Blank et al. (2000) developed a special technique to try and answer this question. They used an 80-mm cannon to produce the shock waves the shocked solution contained the two amino acids lysine and norvaline, which had been found in the Murchison meteorite. Small amounts of the amino acids survived the bombardment , lysine seeming to be a little more robust. In other experiments, the amino acids aminobutyric acid, proline and phenylalanine were subjected to shock waves the first of the three was most stable, the last the most reactive. The products included amino acid dimers as well as cyclic diketopiperazine. The kinetic behaviour of the amino acids differs pressure seems to have a greater effect on the reaction pathway than temperature. As had been recognized earlier, the effect of pressure would have slowed down certain decomposition reactions, such as pyrolysis and decarboxylation (Blank et al., 2001). 

A GC analysis of amino acids requires a derivatisation step to increase the volatility of the amino acids. Generally, norleucine and/or norvaline are the internal standards added to the hydrolysate to check the derivatisation yield. According to the experimental method applied, the limits of detection (LOD) vary in the range 10 100 pg for each amino acid. Regarding the chromatographic columns, as most of the derivatives are esters barely polar compounds the most commonly used are fused-silica capillary columns with a low... 

Norbomen-2-carbaldehyde, bl36 Norbomene, bl35 Norbomylene, bl35 Norcamphor, al04 Norleucine, al82 Norvaline, a248 NT A, n20... 

The interaction with both synthetic and naturally occurring amino acids has been studied extensively glycine (138, 173, 219-221), a-(173, 219) and /3-alanine (138, 220), sarcosine (219), serine (222), aspartic acid (138, 173, 222-226), asparagine (222), threonine (222), proline (219), hydroxyproline (219), glutamic acid (138, 222-225), glutamine (222), valine (219, 227), norvaline (219), methionine (222, 226), histidine (228, 229), isoleucine (219), leucine (219, 230), norleu-cine (219), lysine (222), arginine (222), histidine methyl ester (228), phenylalanine (138, 222), tyrosine (222), 2-amino-3-(3,4-dihydroxy-phenyl jpropanoic acid (DOPA) (222), tryptophan (222), aminoiso-butyric acid (219), 2-aminobutyric acid (219,231), citrulline (222), and ornithine (222). 

An enantioselective synthesis of the natural venom pumiliotoxin C 98 and its unnatural enantiomer was achieved from (/ )-norvaline in a multistep... 

Fig. S6. Separation of D,L-dansyl amino acids. Conditions 0.65 oiAf L 2>isopropyl-dien-Zn(II) 0.17 A NH,Ac to pH 9.0 with aqueous NI 35/65 CH,CN/H,0 T - 30 flowrate 2 tnl/min column 15 cm by 4.6 mm i.d. S iun Hypersil C solutes CySO H -cysteic acid Ser - serine Trp - tryptophan thr - threonine Norval - norvaline Leu w leucine Norleu - norleucine Phe phenylalanine. Detection at 254 nm. Reprinted with permission from LePage ef at. C246), Am/. Chem. Copyright 1979 by the American Chemical Society.

Quantification of the separated amino acids is usually performed by using external calibration or the internal standard method. Due to the large differences in chemical structure exhibited by the various amino acids, there is not a single ideal standard for the overall amino acid profile. Nevertheless, a suitable internal standard must be stable to hydrolysis and offer chromatographic resolution. The most popular choices comprise norleucine, norvaline, and a-amino-n-butanoic acid (AABA) [196]. 

The numerous preparations of mono-, di-, tri-, and hexafluoro derivatives of valine, norvaline, leucine, norleucine, and isoleucine, using classical methods of amino acid chemistry (e.g., amination of an a-bromoacid, " azalactone, Strecker reaction, amidocarbonylation of a trifluoromethyl aldehyde, alkylation of a glycinate anion are not considered here. Pure enantiomers are generally obtained by enzymatic resolution of the racemate, chemical resolution, or asymmetric Strecker reaction. ... 

Nonbranched amino acids substituted by a fluoroalkyl chain on a carbon distant at least one methylene from the amino acid function have been prepared as racemates by various methods." Under nonracemic form, co-perfluoroalkyl norvaline and norleucine (Rf = C2F5 or more) have been prepared by bromination of an anion of a fluorinated chiral oxazolidinone (derived from RfCH2CH2C02H). Substitution of the bromine atom by an azide and subsequent reduction yield the desired amino acids (Figure 5.10)." ... 

R)- und (S)-Norvalin-methylester2 (R)-ct-Methyl norvalin-methy tester2... 

Thus, (2R)-pumiliotoxin C (214) has been prepared from (R)-norvaline (212). The asymmetric center in the triene (213) controls the configuration at three carbon atoms 210). a-Kainic acid, isolated from the algae Digena simplex and Centrocerus clavulatum, was prepared by total synthesis. Its enantioselective synthesis involved a stereocon trolled intramolecular cycloaddition of a (S)-glutamic acid211). Asymmetric cycloadditions also play a decisive role in the synthesis of chiral cytochalasins. In this case 212> the primary chiral information was carried by (S)-alanine and (S)-phenylalanine, respectively. 

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