Chemoselective Ullmann Reaction of α-Trisubstituted Thioamides: Synthesis of Novel 2-Iminobenzothiolanes

Overview

Journal ACS Omega

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Aug 23

PMID 34423225

Authors

Anwesha Bhattacharya

Annaram Thirupathi

Pradeep Natarajan

Saravanan Peruncheralathan

Affiliations

Soon will be listed here.

Abstract

New classes of unexplored benzo[]thiolanes are synthesized from trisubstituted thioamides through copper-catalyzed intramolecular -arylation of thioamides for the first time. This method provides good to excellent yields with fully controlled chemoselectivity. Unusually, iminobenzo[]thiolanes are very stable under mild acidic conditions. A plausible mechanism is proposed for the chemoselective -arylation process.

References

Kawamoto Y, Tomino M, Hiramatsu K, Oyama Y, Hayashi Y . Benzothiophene derivatives as phosphodiesterase 10A (PDE10A) inhibitors: Hit-to-lead studies. Bioorg Med Chem Lett. 2019; 29(11):1419-1422. DOI: 10.1016/j.bmcl.2019.03.021. View

Ma D, Lu X, Shi L, Zhang H, Jiang Y, Liu X . Domino condensation/S-arylation/heterocyclization reactions: copper-catalyzed three-component synthesis of 2-N-substituted benzothiazoles. Angew Chem Int Ed Engl. 2011; 50(5):1118-21. DOI: 10.1002/anie.201005787. View

Chalmers M, Wang Y, Novick S, Sato M, Bryant H, Montrose-Rafizdeh C . Hydrophobic Interactions Improve Selectivity to ERα for Ben-zothiophene SERMs. ACS Med Chem Lett. 2012; 3(3):207-210. PMC: 3349201. DOI: 10.1021/ml2002532. View

Berrade L, Aisa B, Ramirez M, Galiano S, Guccione S, Moltzau L . Novel benzo[b]thiophene derivatives as new potential antidepressants with rapid onset of action. J Med Chem. 2011; 54(8):3086-90. DOI: 10.1021/jm2000773. View

Wada Y, Fujioka H, Kita Y . Synthesis of the marine pyrroloiminoquinone alkaloids, discorhabdins. Mar Drugs. 2010; 8(4):1394-416. PMC: 2866491. DOI: 10.3390/md8041394. View

Huang X, Ding R, Mo Z, Xu Y, Tang H, Wang H . Photocatalytic Construction of S-S and C-S Bonds Promoted by Acridinium Salt: An Unexpected Pathway To Synthesize 1,2,4-Dithiazoles. Org Lett. 2018; 20(16):4819-4823. DOI: 10.1021/acs.orglett.8b01970. View

Kumar Y, Ila H . Synthesis of Substituted Benzo[]thiophenes via Base-Promoted Domino Condensation-Intramolecular C-S Bond Formation. Org Lett. 2021; 23(5):1698-1702. DOI: 10.1021/acs.orglett.1c00085. View

Yang X, Lin H, Matsuo Y . Highly Selective Synthesis of Tetrahydronaphthaleno[60]fullerenes via Fullerene-Cation-Mediated Intramolecular Cyclization. J Org Chem. 2019; 84(24):16314-16322. DOI: 10.1021/acs.joc.9b02618. View

Masuya Y, Tobisu M, Chatani N . Palladium-Catalyzed Synthesis of 2,3-Disubstituted Benzothiophenes via the Annulation of Aryl Sulfides with Alkynes. Org Lett. 2016; 18(17):4312-5. DOI: 10.1021/acs.orglett.6b02055. View

10.

Zhang W, Tao S, Ge H, Li Q, Ai Z, Li X . Construction of 2-Arylbenzo[4,5]thieno[2,3-]thiazole Skeleton via CuCl/S-Mediated Three-Component Reaction. Org Lett. 2020; 22(2):448-452. DOI: 10.1021/acs.orglett.9b04206. View

11.

Matsuzawa T, Hosoya T, Yoshida S . One-step synthesis of benzo[]thiophenes by aryne reaction with alkynyl sulfides. Chem Sci. 2021; 11(35):9691-9696. PMC: 8162113. DOI: 10.1039/d0sc04450d. View

12.

Dang P, Zheng Z, Liang Y . Copper-Catalyzed C(sp)-S Bond and C(sp)-S Bond Cross-Coupling of 2-(2-Iodobenzoyl) Substituted or 2-(2-Iodobenzyl) Substituted 1,2,3,4-Tetrahydroisoquinolines with Potassium Sulfide: Synthesis of Isoquinoline-Fused 1,3-Benzothiazine Scaffolds. J Org Chem. 2017; 82(4):2263-2268. DOI: 10.1021/acs.joc.6b02943. View

13.

Pieroni M, Azzali E, Basilico N, Parapini S, Zolkiewski M, Beato C . Accepting the Invitation to Open Innovation in Malaria Drug Discovery: Synthesis, Biological Evaluation, and Investigation on the Structure-Activity Relationships of Benzo[b]thiophene-2-carboxamides as Antimalarial Agents. J Med Chem. 2017; 60(5):1959-1970. DOI: 10.1021/acs.jmedchem.6b01685. View

14.

Guin J, Varseev G, List B . Catalytic asymmetric protonation of silyl ketene imines. J Am Chem Soc. 2013; 135(6):2100-3. DOI: 10.1021/ja312141b. View

15.

Singh P, Yadav A, Ila H, Junjappa H . Novel Route to 2,3-Substituted Benzo[b]thiophenes via Intramolecular Radical Cyclization. J Org Chem. 2009; 74(15):5496-501. DOI: 10.1021/jo900615p. View

16.

Romagnoli R, Baraldi P, Carrion M, Cara C, Preti D, Fruttarolo F . Synthesis and biological evaluation of 2- and 3-aminobenzo[b]thiophene derivatives as antimitotic agents and inhibitors of tubulin polymerization. J Med Chem. 2007; 50(9):2273-7. DOI: 10.1021/jm070050f. View

17.

Sundaravelu N, Nandy A, Sekar G . Visible Light Mediated Photocatalyst Free C-S Cross Coupling: Domino Synthesis of Thiochromane Derivatives via Photoinduced Electron Transfer. Org Lett. 2021; 23(8):3115-3119. DOI: 10.1021/acs.orglett.1c00806. View

18.

Yao H, Ye L, Zhang H, Li S, Zhang S, Hou J . Molecular Design of Benzodithiophene-Based Organic Photovoltaic Materials. Chem Rev. 2016; 116(12):7397-457. DOI: 10.1021/acs.chemrev.6b00176. View

19.

Janni M, Arora S, Peruncheralathan S . Double heteroannulation of S,N-acetals: a facile access to quinolone derivatives. Org Biomol Chem. 2016; 14(37):8781-8788. DOI: 10.1039/c6ob01568a. View

20.

Ding Q, He X, Wu J . Synthesis of 2-aminobenzothiazole via copper(I)-catalyzed tandem reaction of 2-iodobenzenamine with isothiocyanate. J Comb Chem. 2009; 11(4):587-91. DOI: 10.1021/cc900027c. View