title: Gold(I)-catalyzed cycloisomerizations and alkoxycyclizations of ortho-(alkynyl)styrenes.
abstract: Indenes and related polycyclic structures have been efficiently synthesized by gold(I)-catalyzed cycloisomerizations of appropriate ortho-(alkynyl)styrenes. Disubstitution at the terminal position of the olefin was demonstrated to be essential to obtain products originating from a formal 5-endo-dig cyclization. Interestingly, a complete switch in the selectivity of the cyclization of o-(alkynyl)-α-methylstyrenes from 6-endo to 5-endo was observed by adding an alcohol to the reaction media. This allowed the synthesis of interesting indenes bearing an all-carbon quaternary center at C1. Moreover, dihydrobenzo[a]fluorenes can be obtained from substrates bearing a secondary alkyl group at the β-position of the styrene moiety by a tandem cycloisomerization/1,2-hydride migration process. In addition, diverse polycyclic compounds were obtained by an intramolecular gold-catalyzed alkoxycyclization of o-(alkynyl)styrenes bearing a nucleophile in their structure. Finally, the use of a chiral gold complex allowed access to elusive chiral 1H-indenes in good enantioselectivities.
authors.affiliation: Área de Química Orgánica, Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Pza. Misael Bañuelos s/n, 09001 Burgos (Spain) http://www2.ubu.es/ginves/cien_biotec/sintorg/uk/index.htm.
authors.forename: Ana M
authors.initials: AM
authors.lastname: Sanjuán
authors.forename: Muhammad A
authors.initials: MA
authors.lastname: Rashid
authors.forename: Patricia
authors.initials: P
authors.lastname: García-García
authors.forename: Alberto
authors.initials: A
authors.lastname: Martínez-Cuezva
authors.forename: Manuel A
authors.initials: MA
authors.lastname: Fernández-Rodríguez
authors.forename: Félix
authors.initials: F
authors.lastname: Rodríguez
authors.forename: Roberto
authors.initials: R
authors.lastname: Sanz
keywords: asymmetric catalysis; cyclization; cycloisomerization; gold; indenes