Fmoc-L-glutamic acid α-allyl ester
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Fmoc-L-glutamic acid α-allyl ester

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Allyl esters are useful carboxy protecting groups in the synthesis of various cyclic peptides glycopeptides. Allyl esters are cleaved quantitatively under mild conditions using Pd(0) catalyst.

Category
Fmoc-Amino Acids
Catalog number
BAT-003752
CAS number
144120-54-7
Molecular Formula
C23H23NO6
Molecular Weight
409.43
Fmoc-L-glutamic acid α-allyl ester
IUPAC Name
(4S)-4-(9H-fluoren-9-ylmethoxycarbonylamino)-5-oxo-5-prop-2-enoxypentanoic acid
Synonyms
Fmoc-L-Glu-OAll; (S)-4-((((9H-Fluoren-9-yl)methoxy)carbonyl)amino)-5-(allyloxy)-5-oxopentanoic acid; Fmoc-Glu-OAll; Fmoc-L-glutamic acid alpha-allyl ester; L-Fmoc-Glu-OAll; Fmoc-Glu-OAllyl
Appearance
White to off-white powder
Purity
≥ 98% (HPLC)
Density
1.264±0.06 g/cm3
Melting Point
118-133 °C
Boiling Point
652.3±55.0 °C
Storage
Store at 2-8 °C
InChI
InChI=1S/C23H23NO6/c1-2-13-29-22(27)20(11-12-21(25)26)24-23(28)30-14-19-17-9-5-3-7-15(17)16-8-4-6-10-18(16)19/h2-10,19-20H,1,11-14H2,(H,24,28)(H,25,26)/t20-/m0/s1
InChI Key
ORKKMGRINLTBPC-FQEVSTJZSA-N
Canonical SMILES
C=CCOC(=O)C(CCC(=O)O)NC(=O)OCC1C2=CC=CC=C2C3=CC=CC=C13

Fmoc-L-glutamic acid α-allyl ester, a derivative of glutamic acid with wide applicability in peptide synthesis and biochemical endeavors, serves diverse purposes. Here are four key applications of Fmoc-L-glutamic acid α-allyl ester:

Peptide Synthesis: A fundamental element in peptide assembly, Fmoc-L-glutamic acid α-allyl ester acts as a crucial building block. Its Fmoc protecting group facilitates solid-phase peptide synthesis, allowing step-by-step addition of amino acids. Moreover, the α-allyl ester acts as a transient shield that can be selectively removed to enable further modification of the peptide chain, providing flexibility in peptide design.

Structural Biology: In the realm of structural biology, Fmoc-L-glutamic acid α-allyl ester plays a pivotal role in incorporating targeted alterations into peptides and proteins for structural exploration. Researchers can integrate this modified amino acid into protein sequences to investigate folding dynamics and interactions, enabling a deeper understanding of protein structure and function through techniques like NMR and X-ray crystallography, shedding light on the molecular intricacies of biological systems.

Drug Development: Driving innovation in drug development, Fmoc-L-glutamic acid α-allyl ester is instrumental in the creation of peptide-based therapeutics, particularly in crafting pro-drugs and modified peptides with enhanced stability and bioavailability. By tweaking glutamic acid residues in peptide drugs, researchers aim to enhance therapeutic efficacy and target specificity, paving the way for the design of potent and durable peptide-based treatments that hold promise for addressing challenging medical conditions.

Bioconjugate Chemistry: Embraced in the realm of bioconjugate chemistry, Fmoc-L-glutamic acid α-allyl ester serves as a key component in crafting functionalized peptides and proteins. It provides a reactive site for conjugation with diverse molecules such as fluorescent dyes, polymers, or drug compounds. These modifications enable the development of innovative peptide-based probes and delivery systems for applications in research and biomedicine, offering new avenues for exploring and addressing complex biological phenomena.

1. Efficient asymmetric syntheses of α-quaternary lactones and esters through chiral bifunctional sulfide-catalyzed desymmetrizing bromolactonization of α,α-diallyl carboxylic acids
Mana Hiraki, Ken Okuno, Ryuichi Nishiyori, Ahmed A Noser, Seiji Shirakawa Chem Commun (Camb). 2021 Oct 19;57(83):10907-10910. doi: 10.1039/d1cc03874e.
Asymmetric halolactonizations are powerful methods for the syntheses of chiral lactones. Catalytic and highly enantioselective halolactonizations of α-allyl carboxylic acids, however, continue to present a formidable challenge. Herein, we report the chiral bifunctional sulfide-catalyzed desymmetrizing bromolactonizations of α,α-diallyl carboxylic acids. These reactions efficiently produced chiral α-quaternary lactones and esters.
2. Catalytic α-allylation of unprotected amino acid esters
Ping Fang, Mani Raj Chaulagain, Zachary D Aron Org Lett. 2012 Apr 20;14(8):2130-3. doi: 10.1021/ol300665n. Epub 2012 Apr 9.
Catalytic α-allylation of unprotected amino acid esters to produce α-quaternary α-allyl amino acid esters is reported. Catalytic loadings of picolinaldehyde and Ni(II) salts induce preferential reactivity at the enolizable α-carbon of amino acid esters over the free nitrogen with electrophilic palladium π-allyl complexes. Fourteen examples are given. Additionally, the use of chiral ligands to access enantioenriched α-quaternary amino acid esters from racemic precursors is demonstrated by the enantioselective synthesis of α-allyl phenylalanine methyl ester from racemic phenylalanine methyl ester.
3. Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds
Jason R Combs, Yin-Chu Lai, David L Van Vranken Org Lett. 2021 Apr 16;23(8):2841-2845. doi: 10.1021/acs.orglett.1c00229. Epub 2021 Apr 1.
Allyl 2-diazo-2-phenylacetates are shown to react with trimethylsilyl thioethers in the presence of rhodium(II) catalysts to generate α-allyl-α-thio silyl esters. The transformation involves a tandem process involving formal rhodium-catalyzed insertion of the carbene group into the S-Si bond to generate a silyl ketene acetal, followed by a spontaneous Ireland-Claisen rearrangement. The silyl ester products were isolated as the corresponding carboxylic acids after aqueous workup. Intramolecular cyclopropanation of the allyl fragment generally competes with addition of the heteroatom to the carbene center. The reaction occurs under mild conditions and in high yield, allowing for rapid entry into rearrangement tetrasubstituted products. Propargyl esters were shown to generate the corresponding α-allenyl products.
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