2026-05-27T09:18:36Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/38952022-12-19T09:36:20Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594

Sanjuán Cortázar, Ana María Rashid, Muhammad A. García García, Patricia Martínez Cuezva, Alberto Fernández Rodríguez, Manuel A. Rodríguez, Félix Sanz Díez, Roberto 2015-12-10T12:48:00Z 2016-02-09T03:45:06Z 2015-02 0947-6539 http://hdl.handle.net/10259/3895 10.1002/chem.201405789 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 Ministerio de Economia y Competitividad (MINECO) and FEDER (CTQ2010-15358 and CTQ2013-48937-C2-1-P) and Junta de Castilla y Leon (BU237U13) for financial support. A.M.S. thanks the Junta de Castilla y Leon (Consejeria de Educacion) and the Fondo Social Europeo for a PIRTU contract. M.A.R. and P.G.-G. thank MEC for a "Young Foreign Researchers" (SB2009-0186) contract and MINECO for "Juan de la Cierva" contract, respectively This is the peer reviewed version of the following article: Sanjuán, A. M., Rashid, M. A., García-García, P., Martínez-Cuezva, A., Fernández-Rodríguez, M. A., Rodríguez, F. and Sanz, R. (2015), Gold(I)-Catalyzed Cycloisomerizations and Alkoxycyclizations of ortho-(Alkynyl)styrenes. Chem. Eur. J., 21: 3042–3052. doi: 10.1002/chem.201405789, which has been published in final form at 10.1002/chem.201405789. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving application/pdf eng Wiley-VCH Verlag Chemistry-A european journal. 2015. V. 21, n. 7, p. 3042-3052 http://dx.doi.org/10.1002/chem.201405789 info:eu-repo/grantAgreement/MINECO/CTQ2010-15358 info:eu-repo/grantAgreement/MINECO/CTQ2013-48937-C2-1-P info:eu-repo/grantAgreement/MEC/SB2009-0186 info:eu-repo/grantAgreement/JCyL/BU237U13 asymmetric catalysis cyclization cycloisomerization gold indenes Química orgánica Chemistry, Organic Gold(I)-Catalyzed Cycloisomerizations and Alkoxycyclizations of ortho-(Alkynyl)styrenes info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion info:eu-repo/semantics/openAccess