A facile stereoselective synthesis of cis and trans unsaturated dicarba peptides has been established using preformed diaminosuberic acid derivatives as bridging units. In addition, characteristic spectral differences in the (13)C-NMR spectra of the cis- and trans-isomers show that the chemical shift of carbons in the Δ4,5-diaminosuberic acid residue can be used to assign stereochemistry in unsaturated dicarba peptides formed from ring closing metathesis of linear peptide sequences.
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http://dx.doi.org/10.1039/c5cc10540d | DOI Listing |
Molecules
September 2024
Postovsky Institute of Organic Synthesis, Russian Academy of Sciences (Ural Branch), Ekaterinburg 620108, Russia.
Amino acids with unusual types of chirality and their derivatives have recently attracted attention as precursors in the synthesis of chiral catalysts and peptide analogues with unique properties. In this study, we have synthesized a new -carborane-based planar-chiral amino acid, in the molecule of which the amino group is directly bonded to the B(3) atom, and the carboxyl group is attached to the B(9) atom through the CHS(Me) fragment. 3-Amino-9-dimethylsulfonio--carborane, prepared in three steps from 3-amino--carborane in a high yield, was a key intermediate in the synthesis of the target planar-chiral amino acid.
View Article and Find Full Text PDFMar Drugs
June 2023
School of Chemistry, Monash University, Clayton, VIC 3800, Australia.
Recombinant peptide synthesis allows for large-scale production of peptides with therapeutic potential. However, access to dicarba peptidomimetics via sidechain-deprotected sequences becomes challenging with exposed Lewis basicity presented by amine and sulfur-containing residues. Presented here is a combination of strategies which can be used to deactivate coordinative residues and achieve high-yielding Ru-catalyzed ring-closing metathesis.
View Article and Find Full Text PDFMolecules
April 2023
Postovsky Institute of Organic Synthesis, Russian Academy of Sciences (Ural Branch), 620108 Ekaterinburg, Russia.
Short peptides containing the Arg-Gly-Asp (RGD) fragment can selectively bind to integrins on the surface of tumor cells and are attractive transport molecules for the targeted delivery of therapeutic and diagnostic agents to tumors (for example, glioblastoma). We have demonstrated the possibility of obtaining the - and -protected RGD peptide containing 3-amino--carborane and a glutaric acid residue as a linker fragment. The resulting carboranyl derivatives of the protected RGD peptide are of interest as starting compounds in the synthesis of unprotected or selectively protected peptides, as well as building blocks for preparation of boron-containing derivatives of the RGD peptide of a more complex structure.
View Article and Find Full Text PDFJ Pept Sci
July 2023
Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Praha, Czech Republic.
Insulin is a peptide responsible for regulating the metabolic homeostasis of the organism; it elicits its effects through binding to the transmembrane insulin receptor (IR). Insulin mimetics with agonistic or antagonistic effects toward the receptor are an exciting field of research and could find applications in treating diabetes or malignant diseases. We prepared five variants of a previously reported 20-amino acid insulin-mimicking peptide.
View Article and Find Full Text PDFFront Endocrinol (Lausanne)
July 2022
Discipline of Medical Biochemistry, Flinders Health and Medical Research Institute, Flinders University of South Australia, Bedford Park, SA, Australia.
The mechanisms by which insulin activates the insulin receptor to promote metabolic processes and cellular growth are still not clear. Significant advances have been gained from recent structural studies in understanding how insulin binds to its receptor. However, the way in which specific interactions lead to either metabolic or mitogenic signalling remains unknown.
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