Synthesis of 2-Cyanobenzothiazoles Via Pd-Catalyzed/Cu-Assisted C-H Functionalization/Intramolecular C-S Bond Formation from -Arylcyanothioformamides

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2022 Dec 11

PMID 36500519

Authors

Nathan Broudic

Alexandra Pacheco-Benichou

Corinne Fruit

Thierry Besson

Affiliations

Soon will be listed here.

Abstract

We report herein on a catalytic system involving palladium and copper to achieve the cyclization of -arylcyanothioformamides and the synthesis of 2-cyanobenzothiazoles. The C-H functionalization/intramolecular C-S bond formation reaction was achieved in the presence of air, using 2.0 equiv of an inorganic additive (KI). In many cases, the reaction led to a sole product regioselectively obtained in good yields, allowing the synthesis of a wide range of substituted 2-cyanobenzothiazole derivatives, providing valuable building blocks for the design of more complex heterocyclic or molecular labeling systems.

Citing Articles

Novel Thiazole-Fused [4,5-] or [5,4-]Quinazolin-8-ones and Their Quinazoline Analogues: Synthesis and Biological Evaluation.

Broudic N, Pacheco-Benichou A, Corbiere C, Baratte B, Robert T, Bach S Pharmaceuticals (Basel). 2024; 17(11).

PMID: 39598364 PMC: 11597202. DOI: 10.3390/ph17111452.

References

Yuan Y, Liang G . A biocompatible, highly efficient click reaction and its applications. Org Biomol Chem. 2013; 12(6):865-71. DOI: 10.1039/c3ob41241e. View

Inamoto K, Hasegawa C, Hiroya K, Doi T . Palladium-catalyzed synthesis of 2-substituted benzothiazoles via a C-H functionalization/intramolecular C-S bond formation process. Org Lett. 2008; 10(22):5147-50. DOI: 10.1021/ol802033p. View

Irfan A, Batool F, Naqvi S, Islam A, Osman S, Nocentini A . Benzothiazole derivatives as anticancer agents. J Enzyme Inhib Med Chem. 2019; 35(1):265-279. PMC: 6896476. DOI: 10.1080/14756366.2019.1698036. View

Dragulescu-Andrasi A, Kothapalli S, Tikhomirov G, Rao J, Gambhir S . Activatable oligomerizable imaging agents for photoacoustic imaging of furin-like activity in living subjects. J Am Chem Soc. 2013; 135(30):11015-22. PMC: 3771329. DOI: 10.1021/ja4010078. View

Noolvi M, Patel H, Kaur M . Benzothiazoles: search for anticancer agents. Eur J Med Chem. 2012; 54:447-62. DOI: 10.1016/j.ejmech.2012.05.028. View

Kamal A, Syed M, Mohammed S . Therapeutic potential of benzothiazoles: a patent review (2010 - 2014). Expert Opin Ther Pat. 2015; 25(3):335-49. DOI: 10.1517/13543776.2014.999764. View

McCutcheon D, Paley M, Steinhardt R, Prescher J . Expedient synthesis of electronically modified luciferins for bioluminescence imaging. J Am Chem Soc. 2012; 134(18):7604-7. PMC: 3613990. DOI: 10.1021/ja301493d. View

Cao Z, Li D, Zhao L, Liu M, Ma P, Luo Y . Bioorthogonal in situ assembly of nanomedicines as drug depots for extracellular drug delivery. Nat Commun. 2022; 13(1):2038. PMC: 9018704. DOI: 10.1038/s41467-022-29693-8. View

Foucourt A, Hedou D, Dubouilh-Benard C, Desire L, Casagrande A, Leblond B . Design and synthesis of thiazolo[5,4-f]quinazolines as DYRK1A inhibitors, part I. Molecules. 2014; 19(10):15546-71. PMC: 6270991. DOI: 10.3390/molecules191015546. View

10.

Oppedisano F, Catto M, Koutentis P, Nicolotti O, Pochini L, Koyioni M . Inactivation of the glutamine/amino acid transporter ASCT2 by 1,2,3-dithiazoles: proteoliposomes as a tool to gain insights in the molecular mechanism of action and of antitumor activity. Toxicol Appl Pharmacol. 2012; 265(1):93-102. DOI: 10.1016/j.taap.2012.09.011. View

11.

Haider K, Rehman S, Pathak A, Najmi A, Yar M . Advances in 2-substituted benzothiazole scaffold-based chemotherapeutic agents. Arch Pharm (Weinheim). 2021; 354(12):e2100246. DOI: 10.1002/ardp.202100246. View

12.

Strieter E, Blackmond D, Buchwald S . The role of chelating diamine ligands in the goldberg reaction: a kinetic study on the copper-catalyzed amidation of aryl iodides. J Am Chem Soc. 2005; 127(12):4120-1. DOI: 10.1021/ja050120c. View

13.

Moussa Z, Judeh Z, Alzamly A, Ahmed S, Al-Masri H, Al-Hindawi B . Iodine-DMSO mediated conversion of -arylcyanothioformamides to -arylcyanoformamides and the unexpected formation of 2-cyanobenzothiazoles. RSC Adv. 2022; 12(10):6133-6148. PMC: 8981512. DOI: 10.1039/d2ra00049k. View

14.

Jones K, Porterfield W, Rathbun C, McCutcheon D, Paley M, Prescher J . Orthogonal Luciferase-Luciferin Pairs for Bioluminescence Imaging. J Am Chem Soc. 2017; 139(6):2351-2358. PMC: 5452985. DOI: 10.1021/jacs.6b11737. View

15.

Wang W, Gao J . N, S-Double Labeling of N-Terminal Cysteines via an Alternative Conjugation Pathway with 2-Cyanobenzothiazole. J Org Chem. 2019; 85(3):1756-1763. DOI: 10.1021/acs.joc.9b02959. View

16.

Law C, Yeong K . Current trends of benzothiazoles in drug discovery: a patent review (2015-2020). Expert Opin Ther Pat. 2022; 32(3):299-315. DOI: 10.1080/13543776.2022.2026327. View

17.

Liang G, Ren H, Rao J . A biocompatible condensation reaction for controlled assembly of nanostructures in living cells. Nat Chem. 2010; 2(1):54-60. PMC: 3196337. DOI: 10.1038/nchem.480. View

18.

McCutcheon D, Porterfield W, Prescher J . Rapid and scalable assembly of firefly luciferase substrates. Org Biomol Chem. 2014; 13(7):2117-21. PMC: 4318752. DOI: 10.1039/c4ob02529f. View

19.

Inkster J, Colin D, Seimbille Y . A novel 2-cyanobenzothiazole-based (18)F prosthetic group for conjugation to 1,2-aminothiol-bearing targeting vectors. Org Biomol Chem. 2015; 13(12):3667-76. DOI: 10.1039/c4ob02637c. View

20.

Ioka S, Saitoh T, Iwano S, Suzuki K, Maki S, Miyawaki A . Synthesis of Firefly Luciferin Analogues and Evaluation of the Luminescent Properties. Chemistry. 2016; 22(27):9330-7. DOI: 10.1002/chem.201600278. View