title: Striking alkenol versus allenol reactivity: metal-catalyzed chemodifferentiating oxycyclization of enallenols.
abstract: An efficient chemodivergent metal-controlled methodology for the generation of different highly functionalized oxygen heterocycles from common enallenol substrates has been developed. Chemoselectivity control in the O-C functionalization of an enallenol can be achieved through the choice of catalyst: AuCl(3), PdCl(2), and [PtCl(2)(CH(2)=CH(2))](2) exclusively afford dihydrofurans through selective activation of the allenol moiety, whereas FeCl(3) solely gives tetrahydrofurans or tetrahydropyrans through selective activation of the alkenol moiety. We have also shown that a combination of metal-mediated hydroalkoxylation and allenic aminocyclization reactions can lead to a useful preparation of the tetrahydrofuro[3,2-b]piperidine core of the antimalarial alkaloid isofebrifugine. These divergent heterocyclization reactions have been developed experimentally and additionally, their mechanisms have been investigated by a theoretical study.
authors.affiliation: Grupo de Lactamas y Heterociclos Bioactivos, Departamento de Química Orgánica I, Unidad Asociada al CSIC, Facultad de Química, Universidad Complutense de Madrid, E-28040 Madrid, Spain. alcaideb@quim.ucm.es
authors.forename: Benito
authors.initials: B
authors.lastname: Alcaide
authors.forename: Pedro
authors.initials: P
authors.lastname: Almendros
authors.forename: Teresa
authors.initials: T
authors.lastname: Martínez del Campo
authors.forename: María C
authors.initials: MC
authors.lastname: Redondo
authors.forename: Israel
authors.initials: I
authors.lastname: Fernández
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D005663:Furans / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D015394:Molecular Structure; D010984:Platinum / Q000737:chemistry*
chemical_list: D000438:Alcohols; D000475:Alkenes; D005663:Furans; D008670:Metals; D010984:Platinum; D006046:Gold