Glutamic acid 1,5-anhydrides

Garboxy-2-pyrrolidon es from carbobenzoxy-L-glutamic acid 1,5-anhydrides ... 

X Huang, X Luo, Y Roupioz, JW Keillor. Controlled regioselective anilide formation from aspartic and glutamic acid anhydrides. J Org Chem 62, 8821, 1997. 

The strategy for developing chiral metallacycles of Ni or Pd from aspartic and glutamic acids anhydrides is shown in Scheme 22. Func-... 

Similar results were achieved with glutamic acid anhydrides 64 and 65 (Table 2). However, although legioselective formation of a-ami-nobutyric acid was possible (Entries 1, 2, and 4), the formation y-ami-nobutyric acids proceeded with only moderate regioselectivity (Entry 6). 

N-Carboxy- from N Carbobenzoxy-L-glutamic acid anhydrides s. 19, 209 NCOOCH CeHs NCOOH... 

The 7 glutamyl phosphate formed m this step is a mixed anhydride of glutamic acid and phosphoric acid It is activated toward nucleophilic acyl substitution and gives glutamine when attacked by ammonia... 

Synthetic Polymers. Synthetic polymers are versatile and offer promise for both targeting and extracellular-intracellular drug delivery. Of the many soluble synthetic polymers known, the poly(amino acids) [poly(L-lysine), poly(L-aspartic acid), and poly(glutamic acid)], poly(hydroxypropylmethacrylamide) copolymers (polyHPMA), and maleic anhydride copolymers have been investigated extensively, particularly in the treatment of cancers. A brief discussion of these materials is presented. 

FIGURE 6.13 Activation of Na-substituted aspartic or glutamic acid in the presence or absence of amine nucleophile gives the anhydride. Aminolysis of the anhydride gives a mixture of two peptides. [Melville 1935 Bergmann et al., 1936],... 

FIGURE 8.2 Synthesis of isoglutamine by reaction of the mixed anhydride of protected glutamic acid with gaseous ammonia followed by deprotection by hydrogenolysis.11 a = EtOCOCl/Bu3N in dioxane b = anhydrous NH3 c = H2/Pd(CaC03). 

FIGURE 8.4 Synthesis of anilides of A-protected glutamic acid by aminolysis of the anhydride in dimethylsulfoxide, which gives the a-isomers, and in benzene, which gives the a-isomers.18 X = H, Cl, OMe, N02. 

A series of new amino acid derivatives having pendant nucleic acid bases was prepared by the reaction of L-lysine and L-glutamic acid with the nucleic acid bases. These amino acids were further polymerized by using the N-carboxyamino acid anhydride ( NCA ) method. Alternatively, the nucleic acid base substituted poly-L-lysines were also prepared by using polymer reactions which include the reaction of carboxyethyl derivatives of the bases onto poly-L-lysine. Physico-chemical properties of the polymers obtained were given. 

Lipscomb has commented that glutamic acid-245 might act either as a general base or a nucleophile. The available mechanistic information has been reviewed by Kaiser and Kaiser (1972), who postulated that the carboxylate anion of glutamic acid-245 acts as a nucleophile forming an anhydride intermediate [equation (29)]. The divergent D2O solvent isotope effects, =... 

Ring-opening copolymerization was simultaneously investigated with homopolymerization of N-carboxy-a-amino acid anhydrides, NCAs, by Bamford at al Polymerization of a mixture of NCAs of y-ethyl-L-glutamate and sarcosine ... 

Preparation of - -glutamic acid-y-(f-butyl)ester iV-carboxy anhydride... 

D-Glutamic acid-g-(t-butyl)ester N-carboxy anhydride was previously polymerized by Fujimoto et al. (1) in a l,2-dichloroethane/l,4-dioxane mixture using sodium 4-methyl-2-pyrrolidone as initiator. Additional derivatives were... 

Phthalimidoglutaric acid (18), readily prepared from glutamic acid and phthalic anhydride, has served as a precursor for the preparation of several interesting condensation polymers (76MI1110l). For example, it is readily transformed (Scheme 7) into diisocyanate (19), which was utilized for the preparation of a number of optically active polyureas (by reaction with diamines), polyurethanes (by reaction with diols) and polyurea-urethanes (by reaction with amino alcohols). 

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