2026-04-29T03:40:51Zhttps://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 65768d75-f230-4d58-9a38-e70152d15aea 500 Rashid, Muhammad A. 465 600 García García, Patricia 0c6817a7-07ab-499f-877c-c534362475cd 500 Martínez Cuezva, Alberto 344 500 Fernández Rodríguez, Manuel A. 174 500 Rodríguez, Félix bd204e31-71db-407f-8054-c7acbccad8bf 500 Sanz Díez, Roberto 531 500 0000-0003-2830-0892 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 THUMBNAIL Sanjuan-CAEJ_2015.pdf.jpg Sanjuan-CAEJ_2015.pdf.jpg IM Thumbnail image/jpeg 4642 https://riubu.ubu.es/bitstream/10259/3895/4/Sanjuan-CAEJ_2015.pdf.jpg 70ef70c12514852e8a933ad8cc252829 MD5 4 ORIGINAL Sanjuan-CAEJ_2015.pdf Sanjuan-CAEJ_2015.pdf application/pdf 632548 https://riubu.ubu.es/bitstream/10259/3895/1/Sanjuan-CAEJ_2015.pdf 12ec678f0b56b824c5ff6bfd2c849469 MD5 1 LICENSE license.txt license.txt text/plain; charset=utf-8 1362 https://riubu.ubu.es/bitstream/10259/3895/2/license.txt 5d013bfa6e473ff0db22cd82a4d71a70 MD5 2 TEXT Sanjuan-CAEJ_2015.pdf.txt Sanjuan-CAEJ_2015.pdf.txt Extracted text text/plain 64160 https://riubu.ubu.es/bitstream/10259/3895/3/Sanjuan-CAEJ_2015.pdf.txt 089e72a41f1a0ca63cd7ea3c3da6717a MD5 3 10259/3895 oai:riubu.ubu.es:10259/3895 2022-12-19 10:36:20.004 Repositorio Institucional de la Universidad de Burgos bubrep@ubu.es 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