title: Structural diversity from the transannular cyclizations of natural germacrone and epoxy derivatives: a theoretical-experimental study.
abstract: Treatment of germacrone (1) with different electrophiles, and of its epoxy derivatives germacrone-4,5-epoxide (2), germacrone-1,10-epoxide (3) and isogermacrone-4,5-epoxide (4) with Brönsted/Lewis acids and Ti(III), gives rise to a great structural diversity. Thus, by using a maximum of two steps, the production of more than 40 compounds corresponding to 14 skeletons is described. Computational calculations rationalizing the structural divergence produced are also described. Finally, since some of the compounds generated are bioactive natural sesquiterpenes, the mechanisms of formation of these substances will provide new insights in their biosynthesis.
authors.affiliation: Department of Organic Chemistry, Institute of Biotechnology, University of Granada, Avda. Fuente Nueva, s/n, 18071 Granada, Spain.
authors.forename: M Carmen
authors.initials: MC
authors.lastname: Pérez Morales
authors.forename: Julieta V
authors.initials: JV
authors.lastname: Catalán
authors.forename: Victoriano
authors.initials: V
authors.lastname: Domingo
authors.forename: Martín
authors.initials: M
authors.lastname: Jaraíz
authors.forename: M Mar
authors.initials: MM
authors.lastname: Herrador
authors.forename: José F
authors.initials: JF
authors.lastname: Quílez del Moral
authors.forename: José-Luis
authors.initials: JL
authors.lastname: López-Pérez
authors.forename: Alejandro F
authors.initials: AF
authors.lastname: Barrero
mesh_terms: D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry*; D058116:Lewis Acids / Q000737:chemistry; D008962:Models, Theoretical; D015394:Molecular Structure; D045788:Sesquiterpenes, Germacrane / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D004852:Epoxy Compounds; D058116:Lewis Acids; D045788:Sesquiterpenes, Germacrane; C048393:germacrone