Novel Enantiopure δ-thiolactones: Synthesis, Structural Characterization, and Reactivity Studies

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2024 Dec 25

PMID 39720259

Authors

Magdalena Rodriguez Saravia

Veronica Martinez

Franco Vairoletti

Mario Macias

Danilo Davyt

Gonzalo Hernandez Dossi

Graciela Mahler

Affiliations

Soon will be listed here.

Abstract

A new series of chiral δ-thiolactone derivatives have been prepared. These compounds exemplify the acetalic N-C-S reversibility of fused thiazolidines toward the thermodynamic product. The stereochemistry of the synthesized compounds was elucidated using X-ray crystallography, NOESY spectroscopy, and DFT calculations. The aminolysis reaction of the δ-thiolactone was studied with various alkyl amines, which can open the thioester to yield amido thiols in a single step. This reaction has the potential to be applied in the synthesis of bioactive compounds, polymer chemistry, and dynamic combinatorial chemistry, among others fields.

References

El-Faham A, Albericio F . Peptide coupling reagents, more than a letter soup. Chem Rev. 2011; 111(11):6557-602. DOI: 10.1021/cr100048w. View

Villamil V, Rossi M, Mojica M, Hinchliffe P, Martinez V, Castillo V . Rational Design of Benzobisheterocycle Metallo-β-Lactamase Inhibitors: A Tricyclic Scaffold Enhances Potency against Target Enzymes. J Med Chem. 2024; 67(5):3795-3812. PMC: 11447740. DOI: 10.1021/acs.jmedchem.3c02209. View

Skiles J, Suh J, Williams B, Menard P, Barton J, LOEV B . Angiotensin-converting enzyme inhibitors: new orally active 1,4-thiazepine-2,5-diones, 1,4-thiazine-2,5-diones, and 1,4-benzothiazepine-2,5-diones possessing antihypertensive activity. J Med Chem. 1986; 29(5):784-96. DOI: 10.1021/jm00155a032. View

Ferraris D, Majer P, Ni C, Slusher C, Rais R, Wu Y . δ-Thiolactones as prodrugs of thiol-based glutamate carboxypeptidase II (GCPII) inhibitors. J Med Chem. 2013; 57(1):243-7. PMC: 3932958. DOI: 10.1021/jm401703a. View

Reese C, Thompson B, Logan P, Stafford C, Blanton M, Patton D . Sequential and one-pot post-polymerization modification reactions of thiolactone-containing polymer brushes. Polym Chem. 2020; 10(36). PMC: 7047779. DOI: 10.1039/c9py01123d. View

Saiz C, Wipf P, Manta E, Mahler G . Reversible thiazolidine exchange: a new reaction suitable for dynamic combinatorial chemistry. Org Lett. 2009; 11(15):3170-3. PMC: 2736333. DOI: 10.1021/ol901104a. View

Albrecht S, Defoin A, Salomon E, Tarnus C, Wetterholm A, Haeggstrom J . Synthesis and structure activity relationships of novel non-peptidic metallo-aminopeptidase inhibitors. Bioorg Med Chem. 2006; 14(21):7241-57. DOI: 10.1016/j.bmc.2006.06.050. View

Vallee Y, Shalayel I, Ly K, Rao K, De Paepe G, Marker K . At the very beginning of life on Earth: the thiol-rich peptide (TRP) world hypothesis. Int J Dev Biol. 2017; 61(8-9):471-478. DOI: 10.1387/ijdb.170028yv. View

Agouridas V, El Mahdi O, Diemer V, Cargoet M, Monbaliu J, Melnyk O . Native Chemical Ligation and Extended Methods: Mechanisms, Catalysis, Scope, and Limitations. Chem Rev. 2019; 119(12):7328-7443. DOI: 10.1021/acs.chemrev.8b00712. View

10.

Popova T, Krumkacheva O, Burmakova A, Spitsyna A, Zakharova O, Lisitskiy V . Protein modification by thiolactone homocysteine chemistry: a multifunctionalized human serum albumin theranostic. RSC Med Chem. 2021; 11(11):1314-1325. PMC: 8126878. DOI: 10.1039/c9md00516a. View

11.

Hirschbeck V, Gehrtz P, Fleischer I . Regioselective Thiocarbonylation of Vinyl Arenes. J Am Chem Soc. 2016; 138(51):16794-16799. DOI: 10.1021/jacs.6b11020. View

12.

Hinchliffe P, Gonzalez M, Mojica M, Gonzalez J, Castillo V, Saiz C . Cross-class metallo-β-lactamase inhibition by bisthiazolidines reveals multiple binding modes. Proc Natl Acad Sci U S A. 2016; 113(26):E3745-54. PMC: 4932952. DOI: 10.1073/pnas.1601368113. View

13.

Martinez V, Villamil V, Duarte D, Saiz C, Davyt D, Fontana C . Preparation and mechanistic studies of 2-substituted Bisthiazolidines by imine exchange. European J Org Chem. 2021; 2020(9):1084-1092. PMC: 8442850. DOI: 10.1002/ejoc.201901677. View

14.

Chen H, Xiao Y, Yuan N, Weng J, Gao P, Breindel L . Coupling of sterically demanding peptides by β-thiolactone-mediated native chemical ligation. Chem Sci. 2018; 9(7):1982-1988. PMC: 5892351. DOI: 10.1039/c7sc04744d. View

15.

Kremer L, Douglas J, Baulard A, Morehouse C, Guy M, Alland D . Thiolactomycin and related analogues as novel anti-mycobacterial agents targeting KasA and KasB condensing enzymes in Mycobacterium tuberculosis. J Biol Chem. 2000; 275(22):16857-64. DOI: 10.1074/jbc.M000569200. View

16.

Mammadova A, Gyarmati B, Sardi K, Paudics A, Varga Z, Szilagyi A . Thiolated cationic poly(aspartamides) with side group dependent gelation properties for the delivery of anionic polyelectrolytes. J Mater Chem B. 2022; 10(31):5946-5957. DOI: 10.1039/d2tb00674j. View

17.

Villamil V, Saiz C, Mahler G . Thioester deprotection using a biomimetic NCL approach. Front Chem. 2022; 10:934376. PMC: 9441695. DOI: 10.3389/fchem.2022.934376. View

18.

Lysebetten D, Felissati S, Antonatou E, Carrette L, Espeel P, Focquet E . A Thiolactone Strategy for Straightforward Synthesis of Disulfide-Linked Side-Chain-to-Tail Cyclic Peptides Featuring an N-Terminal Modification Handle. Chembiochem. 2018; 19(6):641-646. DOI: 10.1002/cbic.201700323. View

19.

Fargher H, Sherbow T, Haley M, Johnson D, Pluth M . C-H⋯S hydrogen bonding interactions. Chem Soc Rev. 2022; 51(4):1454-1469. PMC: 9088610. DOI: 10.1039/d1cs00838b. View

20.

Cleland W . DITHIOTHREITOL, A NEW PROTECTIVE REAGENT FOR SH GROUPS. Biochemistry. 1964; 3:480-2. DOI: 10.1021/bi00892a002. View