Glutamate derivatives

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. 

Poche DS, Thibodeaux SJ, Rucker VC, Warner IM, Daly WH (1997) Synthesis of novel gamma-alkenyl L-glutamate derivatives containing a terminal C-C double bond to produce polypeptides with pendent unsaturation. Macromolecules 30 8081-8084... 

The cycle is renewed after the cysteine formed in reaction 6 and the glutamate derived from reaction 6 are converted to y-glutamylcysteine via y-glutamylcysteine synthetase (reaction 1). 

The introduction at the C- or N-terminal position of a crown ether unit has been used as a strategy to control the aggregation of poly(benzyl glutamate) derivatives 19 The incorporation of the crown unit at the C-terminal position is performed using (benzo-15-crown-5)-4-amine as initiator of the polymerization of l-G1u(OBz1)-NCA. Physical properties of such crown derivatives can be modulated by the formation of sandwich 2 1 complexes driven by the addition of specific alkali metal ions. In the reported case, the formation of K+ sandwich complex between two C-terminal benzo-15-crown-5 modified helical polypeptides induced aggregation. In a similar approach,f20 addition of Cs+ to 18-crown-6 terminated helical peptides results in the formation of supramolecular assemblies having membrane ion conductivity activities. 

Various antileukemic agents related to methotrexate, such as 5-deazaaminopterin (385), 5-deaza-folic acid (389) <83JOC4852>, 10-deazaaminopterin (386), 10-deazafolic acid (390) <88JOC35>, 5,10-dideazafolic acid (391), 5,10-dideazaaminopterin (387), and its 5,6,7,8-tetrahydro derivative (392) <85JMC914> are also synthetically available by this method. This route is even successful in the preparation of poly glutamate derivatives of antifolates <9iJOC3386>. 

In starvation, the kidney uses glutamine, and glutamate derived from it, as a source of ammonia to buffer ketone bodies that are excreted. Some ammonia. goes to the liver for urea synthesis. The... 

To investigate the possibihty of ordered molecular assemblies forming in ionic liquids, the solubilities of glycolipids. Schemes 11.3 and 11.4, were tested. L-Glutamate derivatives 4 (n= 12, 16) were employed because they are insoluble in water, even at a concentration of 1 mM. It was found that these water-insoluble... 

Chiral membranes have also been used to separate isomers. A cellulose tris(3,5-dimethylphenyl carbamate) has been used to separate an amino alcohol /8-blocker, although the S isomer was obtained in only 55% ee and the R isomer in 23% ee.22 On the other hand, a chiral membrane of a poly(L-glutamate) derivative completely resolved racemic tryptophan.23 Apoenzymes (enzymes lacking their usual cofactor) have been placed in the pores of a membrane consisting of a gold film covered with polypyrrole.24 In one of these, D-phenylalanine passed through five times faster than the L-isomer. (For more detail on membrane separations, see Chap. 7.) This method holds considerable promise for catalytic membrane reactors, especially if the unwanted isomer can be racemized in situ. 

Side-chain halogenated amino acid derivatives are reduced, deuterated, allylated and alkylated with stannanes and related reagents in free-radical processes [53]. Other side-chain functional groups may also be manipulated to produce amino acid radicals [8, 54-58], and, in particular. Barton decarboxylation of aspartate and glutamate derivatives has been applied in this manner (Scheme 8) [55]. Related procedures have been developed to generate amino acid radicals by dehydrox-ylation of hydroxy amino acid derivatives [56]. Hydroxy amino acid derivatives may also be converted to nitrate esters, from which the corresponding alkoxy radi-... 

Figure 6. a. Proton NMR spectrum (360 MHz) of glutamate derived from M. ammo-... 

Kimizuka s group reported that aqueous dispersion of cationic L-glutamate derivatives 39 and 40 with two alkyl tails gives fibrous nanoassemblies with the bilayer structure (Fig. 22). When anionic naphthalene dye 41 was added to the aqueous bilayer of 40 with long undecyl tails, immediate precipitation occurred. Apparently, formation of the hydrophobic ion-pair destabilizes the long-chained ammonium bilayer of 40. On the other hand, 39 with short octyl tails formed a transparent hydrogel in the presence of anionic dye 41... 

Jensen, J.V., Eberhardt, D., and Wendisch, V.F. (2015) Modular pathway engineering of Corynebacterium glutamicum for production of the glutamate-derived compounds ornithine, proline, putrescine, cit-rulline, and arginine. J. Biotechnol, 214, 85-94. 

We screened the cytotoxicity of metal-dithiocarbamate complexes against melanoma cell cultures and found that Cu, Zn and Fe DTC conqjlexes decreases melanoma viability, but that Ni complex enhance it. As the first con5>lexes had low solubility in water, we then investigated several water-soluble DTC Cu conq)lexes, such as the N-methyl glutamate derivative Cu(mgDTC)2, but all were... 

A wide variety of functionality can be incorporated into the substrate acids, such as in the decarboxylation of a-amino acid derivatives which leads to amines (eq Application of this methodology to the appropriate aspartate and glutamate derivatives provides access to the useful radicals (5) which can be trapped in many ways, such as by halides (overall, a Hunsdiecker reaction), as can many other radical species obtained using this chemistry (see below). 

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