We present a transition metal-free approach to 2-N-substituted indenones, cyclopentenones, and 4-carbonyl oxazoles, based on the reaction of 5-acylated N-fluoroalkyl substituted 1,2,3-triazoles (prepared by a three-component click reaction of copper acetylides, fluoroalkyl azides, and acyl chlorides) with Lewis acids aluminium trichloride or boron trifluoride etherate, proceeding via the generation and cyclization of vinyl cations.

Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030 8 128 43 Prague 2 Czech Republic

The Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nam 2 16610 Prague 6 Czech Republic

Zobrazit více v PubMed

Shaw A. Y. Henderson M. C. Flynn G. Samulitis B. Han H. Stratton S. P. Chow H. H. S. Hurley L. H. Dorr R. T. Characterization of Novel Diaryl Oxazole-Based Compounds as Potential Agents to Treat Pancreatic Cancer. J. Pharmacol. Exp. Ther. 2009;331:636–647. PubMed PMC

Ahn J. H. Shin M. S. Jung S. H. Kang S. K. Kim K. R. Rhee S. D. Jung W. H. Yang S. D. Kim S. J. Woo J. R. et al., Indenone Derivatives: A Novel Template for Peroxisome Proliferator- Activated Receptor γ (PPARγ) Agonists. J. Med. Chem. 2006;49:4781–4784. PubMed

Hayashi Y. Ogawa K. Inagaki F. Mukai C. First Total Synthesis of (+)-Indicanone. Org. Biomol. Chem. 2012;10:4747–4751. PubMed

Mehta G. Shinde H. M. An Approach to Seco-Prezizaane Sesquiterpenoids: Enantioselective Total Synthesis of (+)-1S-Minwanenone. J. Org. Chem. 2012;77:8056–8070. PubMed

Harrowven D. C. Newman N. A. Knight C. A. On the Identity of a Neo-Lignan from the Fruits of Virola Sebifera. Tetrahedron Lett. 1998;39:6757–6760.

Desroy N. Denis A. Oliveira C. Atamanyuk D. Briet S. Faivre F. Lefralliec G. Bonvin Y. Oxoby M. Escaich S. et al., Novel HldE-K Inhibitors Leading to Attenuated Gram Negative Bacterial Virulence. J. Med. Chem. 2013;56:1418–1430. PubMed

Joshi S. Mehra M. Singh R. Kakar S. Review on Chemistry of Oxazole Derivatives: Current to Future Therapeutic Prospective. Egypt. J. Basic Appl. Sci. 2023;10:218–239.

Vijay Kumar S. Saraiah B. Misra N. C. Ila H. Synthesis of 2-Phenyl-4,5-Substituted Oxazoles by Copper-Catalyzed Intramolecular Cyclization of Functionalized Enamides. J. Org. Chem. 2012;77:10752–10763. PubMed

Kumar S. V. Acharya A. Ila H. Synthesis of 2,4,5-Trisubstituted Oxazoles with Complementary Regioselectivity from α-Oxoketene Dithioacetals and β-(Methylthio)-β-(Het)Aryl-2-Propenones. J. Org. Chem. 2018;83:6607–6622. PubMed

Rajaguru K. Mariappan A. Suresh R. Manivannan P. Muthusubramanian S. Investigation on the Reactivity of α-Azidochalcones with Carboxylic Acids: Formation of α-Amido-1,3-Diketones and Highly Substituted 2-(Trifluoromethyl)Oxazoles. Beilstein J. Org. Chem. 2015;11:2021–2027. PubMed PMC

Dubovtsev A. Y. Dar’in D. V. Kukushkin V. Y. Three-Component [2+2+1] Gold(I)-Catalyzed Oxidative Generation of Fully Substituted 1,3-Oxazoles Involving Internal Alkynes. Adv. Synth. Catal. 2019;361:2926–2935.

Golling S. Hansjacob P. Bami N. Leroux F. R. Donnard M. Direct Access to 2,3-Disubstituted Amido-Indenones through Annulation of 2-Iodobenzaldehydes with Ynamides. J. Org. Chem. 2022;87:16860–16866. PubMed

Shimizu H. Murakami M. Reaction of 2-Alkynylbenzoyl Cyanides with Carboxylic Acids Producing Functionalized Indenones. Synlett. 2008;12:1817–1820.

Sun J. Zheng G. Xiong T. Zhang Q. Zhao J. Li Y. Zhang Q. Copper-Catalyzed Hydroxyl-Directed Aminoarylation of Alkynes. ACS Catal. 2016;6:3674–3678.

Mokar B. D. Huple D. B. Liu R. S. Gold-Catalyzed Intermolecular Oxidations of 2-Ketonyl-1-Ethynyl Benzenes with N-Hydoxyanilines to Yield 2-Aminoindenones via Gold Carbene Intermediates. Angew. Chem., Int. Ed. 2016;55:11892–11896. PubMed

Sau S. Ghosh A. Shankar M. Gogoi M. P. Sahoo A. K. Cobalt-Catalyzed Thioamide Directed C(Arene)-H Annulation with Ynamide: Regioselective Access to 2-Amidoindenones. Org. Lett. 2022;24:9508–9513. PubMed

Wang Z. Reinus B. J. Dong G. Catalytic Intermolecular β-C–H Alkenylation of α-Enamino-Ketones with Simple Alkynes. Chem. Commun. 2014;50:5230–5232. PubMed

Ottinger H. Soldo T. Hofmann T. Systematic Studies on Structure and Physiological Activity of Cyclic α-Keto Enamines, a Novel Class of “Cooling” Compounds. J. Agric. Food Chem. 2001;49:5383–5390. PubMed

Li Y. Zhang R. Bi X. Fu J. Multifunctionalization of Unactivated Cyclic Ketones via Synergistic Catalysis of Copper and Diarylamine: Access to Cyclic α-Enaminone. Org. Lett. 2018;20:1207–1211. PubMed

Balsells J. Vazquez J. Moyano A. Pericas M. A. Riera A. Low-Energy Pathway for Pauson-Khand Reactions: Synthesis and Reactivity of Dicobalt Hexacarbonyl Complexes of Chiral Ynamines. J. Org. Chem. 2000;65:7291–7302. PubMed

Shnigirev R. B. Ushakov I. A. Semenov V. A. Rulev A. Y. Reactions of α-Functionally Substituted Enals with Terminal Alkynes: Unexpected Assembly of 2-Amino-2-Cyclopentenones. J. Org. Chem. 2023;88:4886–4890. PubMed

Rigby J. H. Wang Z. Synthesis of Highly Substituted Cyclopentenones via the [4 + 1] Cycloaddition of Nucleophilic Carbenes and Vinyl Ketenes. Org. Lett. 2003;5:263–264. PubMed

Blastik Z. E. Voltrová S. Matoušek V. Jurásek B. Manley D. W. Klepetářová B. Beier P. Azidoperfluoroalkanes: Synthesis and Application in Copper(I)-Catalyzed Azide–Alkyne Cycloaddition. Angew. Chem., Int. Ed. 2017;56:346–349. PubMed

Bakhanovich O. Beier P. Synthesis, Stability and Reactivity of α-Fluorinated Azidoalkanes. Chem.–Eur. J. 2020;26:773–782. PubMed

Markos A. Matoušek V. Beier P. Fluoroalkyl Azides and Triazoles: Unlocking a Novel Chemical Space. Aldrichimica Acta. 2022;55:37–44.

Markos A. Voltrová S. Motornov V. Tichý D. Klepetářová B. Beier P. Stereoselective Synthesis of (Z)-β-Enamido Triflates and Fluorosulfonates from N-Fluoroalkylated Triazoles. Chem.–Eur. J. 2019;25:7640–7644. PubMed

Markos A. Janecký L. Klepetářová B. Pohl R. Beier P. Stereoselective Synthesis of (Z)-β-Enamido Fluorides from N-Fluoroalkyl- And N-Sulfonyl-1,2,3-Triazoles. Org. Lett. 2021;23:4224–4227. PubMed

Markos A. Janecký L. Chvojka T. Martinek T. Martinez-Seara H. Klepetářová B. Beier P. Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N-Alkenyl Compounds. Adv. Synth. Catal. 2021;363:3258–3266.

Janecký L. Markos A. Klepetářová B. Beier P. Lewis-Acid-Mediated Intramolecular Cyclization of 4-Aryl-5-Allyl-1,2,3-Triazoles to Substituted Cyclopentene Derivatives. J. Org. Chem. 2023;88:1155–1167. PubMed

Corcoran J. C. Guo R. Xia Y. Wang Y. M. Vinyl Cation-Mediated Intramolecular Hydroarylation of Alkynes Using Pyridinium Reagents. Chem. Commun. 2022;82:11523–11526. PubMed PMC

Wu Y. M. Deng J. Li Y. Chen Q. Y. Regiospecific Synthesis of 1,4,5-Trisubstituted-1,2,3-Triazole via One-Pot Reaction Promoted by Copper(I) Salt. Synthesis. 2005;8:1314–1318.

Voltrová S. Muselli M. Filgas J. Matoušek V. Klepetářová B. Beier P. Synthesis of Tetrafluoroethylene-and Tetrafluoroethyl-Containing Azides and Their 1,3-Dipolar Cycloaddition as Synthetic Application. Org. Biomol. Chem. 2017;15:4962–4965. PubMed

Shaitanova E. Matoušek V. Herentin T. Adamec M. Matyáš R. Klepetářová B. Beier P. Synthesis and Cycloaddition Reactions of 1-Azido-1,1,2,2-Tetrafluoroethane. J. Org. Chem. 2023;88:14969–14977. PubMed PMC

Reactivity of 2H-Azirines in Copper-Catalyzed Azide-Alkyne Cycloaddition Reactions

Transformation of 5-acylated N-fluoroalkyl-1,2,3-triazoles to trifluoromethylated ring-fused isoquinolines, 1,3-oxazines, and 1,3-oxazin-6-ones via ketenimines