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Álvarez-Calero JM, Ruiz E, López-Pérez JL, et al. 15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study. J Org Chem. 2018;83(10):5480-5495doi: 10.1021/acs.joc.8b00407.
Álvarez-Calero, J. M., Ruiz, E., López-Pérez, J. L., Jaraíz, M., Rubio, J. E., Jorge, Z. D., Suárez, M., & Massanet, G. M. (2018). 15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study. The Journal of organic chemistry, 83(10), 5480-5495. https://doi.org/10.1021/acs.joc.8b00407
Álvarez-Calero, José María, et al. "15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study." The Journal of organic chemistry vol. 83,10 (2018): 5480-5495. doi: https://doi.org/10.1021/acs.joc.8b00407
Álvarez-Calero JM, Ruiz E, López-Pérez JL, Jaraíz M, Rubio JE, Jorge ZD, Suárez M, Massanet GM. 15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study. J Org Chem. 2018 May 18;83(10):5480-5495. doi: 10.1021/acs.joc.8b00407. Epub 2018 May 03. PMID: 29694044.
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J Org Chem. 2018 May 18;83(10):5480-5495. doi: 10.1021/acs.joc.8b00407. Epub 2018 May 03.

15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study.

The Journal of organic chemistry

José María Álvarez-Calero, Enrique Ruiz, José Luis López-Pérez, Martín Jaraíz, José E Rubio, Zacarías D Jorge, Margarita Suárez, Guillermo M Massanet

Affiliations

  1. Departamento de Química Orgánica, Facultad de Ciencias , Universidad de Cádiz , Puerto Real, Cádiz 11510 , Spain.
  2. Departamento de Química, Instituto de Ciencias Básicas , Universidad Técnica de Manabí (UTM) , Avenida Urbina y Che Guevara , Portoviejo , Manabí 130103 , Ecuador.
  3. Laboratorio de Síntesis Orgánica, Facultad de Química , Universidad de La Habana , La Habana 10400 , Cuba.
  4. Departamento de Farmacología, Facultad de Medicina , Universidad de Panamá , Ciudad de Panamá 3366 , República de Panamá.
  5. Departamento de Ciencias Farmacéuticas, IBSAL-CIETUS , Universidad de Salamanca , Avda. Campo Charro s/n , Salamanca 37007 , Spain.
  6. Departamento de Electrónica , Universidad de Valladolid , Paseo Belén 15 , Valladolid 47011 , Spain.

PMID: 29694044 DOI: 10.1021/acs.joc.8b00407

Abstract

A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as eudesmanolides, guaianolides, amorphanolides, or other germacranolides. The cyclization that gives guaianolides can be considered a biomimetic route to this type of sesquiterpene lactones. The use of acetone as a solvent changes the reactivity of the two starting germacranolides to the acid catalysts, with a 4,15-diol acetonide being the main product obtained. The δ-amorphenolide obtained by intramolecular cyclization of this acetonide is a valuable intermediate for accessing the antimalarials artemisinin and its derivatives. Mechanistic proposals for the transformations are raised, and to provide support them, quantum chemical calculations [DFT B3LYP/6-31+G(d,p) level] were undertaken.

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