γ-Fluorinated analogues of glutamic acid and glutamine

@article{Dave2003FluorinatedAO,
  title={$\gamma$-Fluorinated analogues of glutamic acid and glutamine},
  author={Rajesh H. Dave and Bernard Badet and Patrick Meffre},
  journal={Amino Acids},
  year={2003},
  volume={24},
  pages={245-261}
}
Summary. γ-Fluorinated analogues of glutamic acid and glutamine are compounds of biological interest. Syntheses of such compounds are extensively reviewed in this article. 4-Fluoroglutamic acid was prepared as a mixture of racemic diastereomers by Michael reaction, inverse-Michael reaction or by electrophilic / nucleophilic fluorination. Optically enriched 4-fluoroglutamic acids were obtained by several resolution techniques as well as by asymmetric methodologies using the chiral pool. 4… Expand

Figures from this paper

γ-Fluorophenyl-GABA derivatives from fluorobenzonitriles in high diastereomeric and enantiomeric excess
Abstract An enantioselective synthesis of α-fluoroaryl homoallylic amines in 52–71% yields and 76–93% enantioselectivities has been achieved via the allylboration of the corresponding fluorinated NExpand
Bacterial defluorination of 4-fluoroglutamic acid
TLDR
Investigations on the degradation of 4-fluoroglutamate by bacteria revealed that only the l-isomer was degraded, and the activity was located in the soluble fraction of cell extracts, thus it was observed that equimolar concentrations of fluoride ion and ammonia were generated. Expand
Synthesis of optically pure 4-fluoro-glutamines as potential metabolic imaging agents for tumors.
TLDR
Preliminary cell uptake and inhibition studies using the 9L tumor cells and SF188(Bcl-xL) tumor cells provided strong evidence for their potential application in conjunction with positron emission tomography (PET) for in vivo imaging of tumors, which use glutamine as an alternative energy source. Expand
Asymmetric synthesis of deuterated and fluorinated aromatic α,α-disubstituted amino acid derivatives
We herein present organocatalytic approaches to synthesize fluorinated and deuterated α-substituted phenylglycine derivatives. Whereas the addition of diethyl azodicarboxylate to fluorinatedExpand
Lactam ring stability of stereoisomers of 4-amino-substituted pyroglutamic acids in acidic medium
The acid hydrolysis of the lactam ring of cis and trans stereoisomers of 4-(1-piperidyl)-, 4-dibenzylamino-, 4-[(methyl)(phenyl)amino]-, 4-phenylamino-, and 4-(4-methoxyphenyl)-aminopyroglutamicExpand
Diastereodivergent hydroxyfluorination of cyclic and acyclic allylic amines: synthesis of 4-deoxy-4-fluorophytosphingosines.
A diastereodivergent hydroxyfluorination protocol enabling the direct conversion of some conformationally biased allylic amines to the corresponding diastereoisomeric amino fluorohydrins has beenExpand
Chemoenzymatic synthesis of each enantiomer of orthogonally protected 4,4-difluoroglutamic acid: a candidate monomer for chiral Brønsted acid peptide-based catalysts.
TLDR
4,4-Difluoroglutamic acid, in a suitably protected form, is shown to exhibit enhanced catalytic activity in both an oxidation reaction and a reduction reaction, in comparison to the analogous glutamic acid derivative. Expand
The conformers of 3-fluoroalanine. A theoretical study.
Quantum chemical calculations (DFT, SCS-MP2) show that the relative energies of the four principal alanine conformations are only marginally altered by the introduction of a single fluorineExpand
Ring opening reactions of cyclic sulfamidates. Synthesis of β-fluoroaryl alanines and derivatives of 4,4-difluoroglutamic acid
Abstract Ring opening reactions of 1 with copper complex formed between Cu, TMEDA and BrCF2CO2Et lead to optically active 4,4-difluoroglutamic acid derivatives 11a-d in moderate yields. Reaction ofExpand
Highly regio- and stereo-selective carbometallation reaction of fluorine-containing internal acetylenes with organocopper reagents
Abstract The carbometallation reactions of fluoroalkylated internal alkynes with various organocopper reagents derived from organolithium, Grignard, and organozinc reagents were examined. AllExpand
...
1
2
3
...

References

SHOWING 1-10 OF 80 REFERENCES
Fluorine containing amino acids and their derivatives. 7. Synthesis and antitumor activity of α- and γ-substituted methotrexate analogs
Abstract Three types of reactions of α-substituted malonates, difluoromethylation, alkylation with n,n,n-trifluoroalkyl sulfonates, and Michael addition to 2-substituted-acrylates, convenientlyExpand
Syntheses ofγ-fluoro-α-amino acids
TLDR
Optically activeγ-fluoro-α-amino acids were synthesized alternatively by phase transfer catalysis with N-benzyl-cinchonium chloride or using an auxiliary-directed asymmetric alkylation of the imine derived from (R)-(+)-camphor or (R-(+-2-hydroxypinan-3-one). Expand
Electrophilic fluorination of pyroglutamic acid derivatives: application of substrate-dependent reactivity and diastereoselectivity to the synthesis of optically active 4-fluoroglutamic acids.
Electrophilic fluorination of enantiomerically pure 2-pyrrolidinones (4) derived from (L)-glutamic acid has been investigated as a method for the synthesis of single stereoisomers of 4-fluorinatedExpand
Preparative separation of 4-fluoroglutamic acid stereoisomers
Abstract A method for separation of 4-fluoroglutamic acid stereoisomers, based on the fractional crystallization of their suitable derivatives, has been developed. The synthetically prepared 1:1Expand
The diastereomers of -fluoroglutamate: complementary structural analogues.
TLDR
Preliminary kinetic studies with several of these enzymes normally reactive with glutamate indicate that the threo tends to be more reactive than the erythro diastereomer, and possible biological and biochemical applications of these glutamate analogues are discussed. Expand
Fluorinated gamma-aminobutyric acid. Enzymatic synthesis and biological activity of a potentially useful analogue.
TLDR
γ-Fluoroglutamate inhibits the glutamate decarboxylase from calf brain at concentrations comparable to the Km of this enzyme for glutamate (10-2 M) and inhibits the uptake of γ-aminobutyric acid in a nerve-muscle preparatiom from lobster. Expand
Chemistry of 4-fluoroglutamic acid. Part 4. Resolution of the racemic erythro and threo forms through their diastereomeric salts
Abstract Racemic erythro -(2 S , 4 R ; 2 R , 4 S )-4-fluoroglutamic acid was successfully resolved, without derivatization, by combination with cinchonine under formation of a sparingly soluble saltExpand
Syntheses of fluorinated amino acids: from the classical to the modern concept
SummaryA survey of the synthetic pathways leading to the fluorine-containing analogues of amino acids is given. From the great number of syntheses the typical examples are selected and divided intoExpand
Synthesis and biological activity of folic acid and methotrexate analogues containing L-threo-(2S,4S)-4-fluoroglutamic acid and DL-3,3-difluoroglutamic acid.
TLDR
Replacement of the glutamate moiety of methotrexate and folic acid with 4-fluoroglutamic acid and 3,3-difluoroglUTamic acid results in folates and antifolates with altered polyglutamylation activity. Expand
Influence of Stereoisomers of 4-Fluoroglutamate on Rat Brain Glutamate Decarboxylase
TLDR
Inhibition of rat brain glutamate decarboxylase (GAD, EC 4.1.15) by individual stereoiso-mers of 4-fluoroglutamate (4-F-Glu) and 2-fluoro-4-aminobutyrate (2-F -GABA) was studied and the influence of all stereoisomers was reversible as shown by dialysis. Expand
...
1
2
3
4
5
...