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

Gold(I)-Catalyzed Cycloisomerizations and Alkoxycyclizations of ortho-(Alkynyl)styrenes Sanjuán Cortázar, Ana María Rashid, Muhammad A. García García, Patricia Martínez Cuezva, Alberto Fernández Rodríguez, Manuel A. Rodríguez, Félix Sanz Díez, Roberto asymmetric catalysis cyclization cycloisomerization gold indenes Química orgánica Chemistry, Organic 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 2015-12-10T12:48:00Z 2016-02-09T03:45:06Z 2015-02 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion 0947-6539 http://hdl.handle.net/10259/3895 10.1002/chem.201405789 eng 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 info:eu-repo/semantics/openAccess application/pdf Wiley-VCH Verlag