Nan Lu*, Chengxia Miao and Xiaozheng Lan

College of Chemistry and Material Science, Shandong Agricultural University, Shandong Prov., P.R. China

*Corresponding Author: Nan Lu, College of Chemistry and Material Science, Shandong Agricultural University, Shandong Prov., P.R. China.

Received: January 25, 2023; Published: February 20, 2023

Abstract

The mechanism is investigated for cascade benz annulation of N-(3-(2-(4-Methoxybenzoyl)phenyl)prop-2-yn-1-yl)benzamide catalyzed by Ag(I). The oxonium-ion generation and water nucleophilic addition induces ring opening hydroxylation, dual ketonization giving 1,5-diketone intermediate. Mediated by acid, the intramolecular cyclization, water elimination affords β-naphthol, from which the nucleophilic cyclization dehydration provides desired product naphthooxazole. The side reaction of acid-activated 5-exo-dig cyclization is accompanied by synergetic synchronous hydrolysis yielding indenone. The promotion of Ag(I) lies in the absolute energy and activation barrier decrease of oxonium-ion generation and water nucleophilic addition. The mediation of acid exists in intramolecular cyclization, nucleophilic cyclization dehydration and 5-exo-dig cyclization. The solvent influence of acid is smaller than Ag(I) from the reduction degree. These results are supported by Multiwfn analysis on FMO of specific TSs and MBO value of vital bonding, breaking.

Keywords: Oxazole-benzannulation; Naphtho[2,3‑d]oxazole; Oxonium-Ion; 5-exo-dig; Cyclization Dehydration

References

1. Lamb YN., et al. “Tafamidis: a review in transthyretin amyloidosis with polyneuropathy”. Drugs 79.8 (2019): 863-874.
2. Singh S., et al. “Recent Advances in the Development of Pharmacologically Active Compounds That Contain a Benzoxazole Scaffold”. The Asian Journal of Organic Chemistry 4.2 (2015): 1338-1361.
3. Jiao WH., et al. “Cinerols, Nitrogenous Meroterpenoids from the Marine Sponge Dysidea cinerea”. The Journal of Natural Products 9 (2019): 2586-2593.
4. Sasmal S., et al. “A First Synthesis of Bis (Benzoxazole) Natural Products: Nataxazole and AJI9561 via Benzoxazole C-H Activation”. Synthesis 47.3 (2015): 711-3716.
5. Pal S., et al. “Benzoxazole Alkaloids: Occurrence, Chemistry, and Biology”. Alkaloids Chemistry and Biology 79 (2018): 71-137.
6. Ouyang H., et al. “An E. coli-Based Biosynthetic Platform Expands the Structural Diversity of Natural Benzoxazoles”. ACS Synthetic Biology 10.9 (2021): 2151-2158.
7. Li Z., et al. “One-Pot Synthesis of 3‑Difluoromethyl Benzoxazole-2-thiones”. Organic Letter 20.20 (2018): 6407-
8. Zhang MC., et al. “Cu-catalyzed Asymmetric Dearomative [3 + 2] Cyclo-addition Reaction of Benzazoles with Aminocyclopropanes”. Chemistry 5.1 (2019): 156-167.
9. Tian ZY., et al. “Pd/Cu-Catalyzed C-H/C-H Cross Coupling of (Hetero)Arenes with Azoles through Arylsulfonium Intermediates”. Organic Letter 23.11 (2021): 4400-4405.
10. Pipaliya BV., et al. “Ruthenium (II) Catalyzed C (sp2)-H Bond Alkenylation of 2-Arylbenzo [d] oxazole and 2-Arylbenzo [d] thiazole with Unactivated Olefins”. Chemistry Asian Journal 16.1 (2021): 87-96.
11. Sagud I., et al. “Photochemical Approach to Naphthoxazoles and Fused Heterobenzoxazoles from 5- (Phenyl/heteroarylethenyl)oxazoles”. Organic Chemistry 76.8 (2011): 2904–2908.
12. Li M., et al. “N‑Phenoxyamides as Multitasking Reagents: Base-Controlled Selective Construction of Benzofurans or Dihydrobenzofuro[2,3‑d]oxazoles”. The Journal of Organic Chemistry 84.13 (2019): 8523-
13. Ma X., et al. “Asymmetric Alkyl and Aryl/Azolation of Alkenes via a Single Cu (I) Complex”. ACS Catalyst 11.9 (2021): 5108-5118.
14. Zhang J., et al. “Thiol substrate-promoted dehydrogenative cyclization of arylmeth-yl thiols with ortho-substituted amines: a universal approach to heteroaromatic compounds”. Organic Chemistry Frontiers Journal 6.13 (2019): 2844-2849.
15. Wu X., et al. “Palladium-Catalyzed Direct Cyclopropylation of Hetero-cycles”. Angewandte Chemie International Edition 54.33 (2015): 9601-9605.
16. Ma X., et al. “Visible Light-Induced Copper-Catalyzed C-H Arylation of Benzoxazoles”. Chinese Journal of Chemistry 38.11 (2020): 1299-1303.
17. Li C., et al. “Light-Promoted Copper-Catalyzed Enantioselective Alkylation of Azoles”. Angewandte Chemie International Edition 60.4 (2021): 2130-2134.
18. Qiao X., et al. “Delivering 2-Aryl Benzoxazoles through Metal-Free and Redox-Neutral De-CF3 Process”. The Journal of Organic Chemistry 86.19 (2021): 13548-13558.
19. Thongsornkleeb C., et al. “Utilization of ortho-alkynylarylcarbonyl derivatives for creating structurally diverse chemical compounds”. Organic and Biomolecular Chemistry 19.27 (2021): 5982-5998.
20. Pradhan TR., et al. “An Overview of Water-Mediated Alkyne Functionalization by Neighboring Group Participation of Carbonyl Groups”. Advanced Synthesis and Catalysis 362.22 (2020): 4833-4860.
21. Jaithum K., et al. “Diastereoselective Synthesis of Spirocyclic Ether from ortho -Carbonylarylacetylenols via Silver-Catalyzed Cyclization under Acidic Conditions”. Advanced Synthesis and Catalysis 363.15 (2021): 3812-3834.
22. Laohapaisan P., et al. “Ag (I)-Catalyzed/Acid-Mediated Cascade Cyclization of ortho-Alkynylaryl-1, 3-dicarbonyls to Access Arylnaphthalenelactones and Furanonaphthol Libraries via Aryl-Disengagement”. Chemistry - Asian Journal 17.1 (2022): e202101212-1-e202101212-15.
23. Rodphon W., et al. “Synthesis of Naphtho[2,3‑d]oxazoles via Ag (I) Acid-Mediated Oxazole-Benzannulation of ortho-Alkynylamidoarylketones”. The Journal of Organic Chemistry (2020).
24. Á lvarez-Corral M., et al. “Silver-mediated synthesis of heterocycles”. Chemical Review 108.8 (2008): 3174-3198.
25. Fang G., et al. “Silver-catalysed reactions of alkynes: recent advances”. Chemical Society Reviews 44.22 (2015): 8124-8173.
26. Frisch MJ., et al. Gaussian 09, Revision B.01, Gaussian, Inc, Wallingford, CT (2009).
27. Hay PJ., et al. “Ab initio effective core potentials for molecular calculations-potentials for the transition-metal atoms Sc to Hg”. The Journal of Chemical Physics 82.1 (1985): 270-283.
28. Lv H., et al. “Ionic Liquid Catalyzed C-C Bond Formation for the Synthesis of Poly substituted Olefins”. European Journal of Organic Chemistry 45 (2022): e202201222 .
29. Zhuang H., et al. “Bu4NHSO4‐Catalyzed Direct N‐Allylation of Pyrazole and its Derivatives with Allylic Alcohols in Water: A Metal‐free, Recyclable and Sustainable System”. Advanced Synthesis and Catalysis 363.24 (2021): 5461-5472.
30. Lu N., et al. “Theoretical investigation on transformation of Cr (II) to Cr (V) complexes bearing tetra-NHC and group transfer reactivity”. International Journal of Quantum Chemistry 120 (2020): e26340.
31. Lu N., et al. “Theoretical investigation on the mechanism and enantioselectivity of organocatalytic asymmetric Povarov reactions of anilines and aldehydes”. International Journal of Quantum Chemistry 120 (2020):
32. Frenking G., et al. “The Nature of the Bonding in Transition-Metal Compounds”. Chemical Review 100.2 (2000): 717-774.
33. Becke AD. “Density-functional thermochemistry. IV. A new dynamical correlation functional and implications for exact-exchange mixing”. The Journal of Chemical Physics 104.3 (1996): 1040-1046.
34. Lee CT., et al. “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density”. Physical Review B 37.2 (1988): 785-789.
35. Tapia O. “Solvent effect theories: Quantum and classical formalisms and their applications in chemistry and biochemistry”. Journal of Mathematical Chemistry 10.1 (1992): 139-181.
36. Tomasi J., et al. “Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent”. Chemical Review 94.7 (1994): 2027-2094.
37. Simkin BY., et al. “Quantum Chemical and Statistical Theory of Solutions—A Computational Approach”. Ellis Horwood, London (1995).
38. Tomasi J., et al. “Quantum Mechanical Continuum Solvation Models”. Chemical Review 105.8 (2005): 2999-3093.
39. Marenich AV., et al. “Universal slovation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions”. The Journal of Physical Chemistry B 113.18 (2009): 6378-6396.
40. Reed AE., et al. “Natural population analysis”. The Journal of Chemical Physics 83.2 (1985): 735-746.
41. Reed AE., et al. “Intermolecular interactions from a natural bond orbital donor-acceptor view point”. Chemical Review 88.6 (1988): 899-926.
42. Foresman, JB., et al. “Exploring Chemistry with Electronic Structure Methods”. 2^nd, Gaussian, Inc., Pittsburgh (1996).
43. Lu T., et al. “Multiwfn: A multifunctional wavefunction analyzer”. Journal of Computational Chemistry 33.5 (2012): 580-592.

Citation

Citation: Nan Lu., et al. “Theoretical Investigation of Ag(I) Acid-catalysed Cascade Benz Annulation of N-(3-(2-(4-Methoxybenzoyl)phenyl)prop-2-yn-1-yl)benzamide for Synthesis of Naphthooxazole". Acta Scientific Pharmaceutical Sciences 7.3 (2023): 11-23.

Copyright

Copyright: © 2022 Nan Lu., et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.