2026-04-29T01:16:56Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/55312021-11-02T12:05:30Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594

Virumbrales, Cintia 578 500 0000-0003-0211-8988 Suarez Pantiga, Samuel 544 500 Marín Luna, Marta 45e13731-b932-44d7-afc4-e48cb9c88a93 500 Silva López, Carlos 0ee5b0c9-6148-4e20-8d10-a4196558fb1c 500 Sanz Díez, Roberto 531 500 2020-10-29T10:46:57Z 2020-10-29T10:46:57Z 2020-07 0947-6539 http://hdl.handle.net/10259/5531 10.1002/chem.202001296 1521-3765 The first general regio‐ and stereoselective 5‐exo gold(I)‐catalyzed alkoxycyclization of a specific class of 1,5‐enynes such as 1,3‐dien‐5‐ynes has been described, despite 1,5‐enynes being known to almost invariably proceed via endo cyclizations under gold‐catalysis. The configuration of the terminal alkene in the starting 1,3‐dien‐5‐yne plays a crucial role on the regiochemical outcome of the reaction. A wide variety of interesting alkoxy‐functionalized alkylidenecyclopentenes have been synthesized from 1‐monosubstituted (E)‐1,3‐dien‐5‐ynes. On the contrary, the corresponding Z isomers evolve affording formal 6‐endo cyclization products. In addition, mechanistic exploration supports a highly stabilized carbocation as a key intermediate instead of a highly constrained cyclopropyl gold carbene from E isomers, and also accounts for the well differentiated reactivity observed between both E/Z geometrical isomers as well as for the stereochemical outcome of the reaction. Ministerio de Ciencia eInnovacinand FEDER (CTQ2016-75023-C2-1-P and 2-P), Junta de Castilla yLenand FEDER (BU291P18) and Xunta de Galiza (ED431C2017/70and ED431E 2018/07) application/pdf eng Wiley Chemistry – A European Journal. 2020, V. 26, n. 38, 8443-8451 https://doi.org/10.1002/chem.202001296 info:eu-repo/grantAgreement/MICINN/CTQ2016-75023-C2-1-P info:eu-repo/grantAgreement/MICINN/CTQ2016-75023-C2-2-P info:eu-repo/grantAgreement/JCyL/BU291P18 info:eu-repo/grantAgreement/XG/ED431C2017/70 info:eu-repo/grantAgreement/XG/ED431E 2018-07 Química orgánica Chemistry, Organic Unlocking the 5‐ exo Pathway with the Au I ‐Catalyzed Alkoxycyclization of 1,3‐Dien‐5‐ynes info:eu-repo/semantics/article info:eu-repo/semantics/submittedVersion info:eu-repo/semantics/openAccess Chemistry – A European Journal 26 38 8443 8451 ORIGINAL Virumbrales-Caej_2020.pdf Virumbrales-Caej_2020.pdf application/pdf 646764 https://riubu.ubu.es/bitstream/10259/5531/1/Virumbrales-Caej_2020.pdf e14d375baa14deffce6029425dfbd762 MD5 1 LICENSE license.txt license.txt text/plain; charset=utf-8 999 https://riubu.ubu.es/bitstream/10259/5531/2/license.txt b295bcbce42e2caabeb0c623d3860c06 MD5 2 THUMBNAIL Virumbrales-Caej_2020.pdf.jpg Virumbrales-Caej_2020.pdf.jpg IM Thumbnail image/jpeg 4617 https://riubu.ubu.es/bitstream/10259/5531/3/Virumbrales-Caej_2020.pdf.jpg 9e7c02e3110ffb4d558bfa83563b7796 MD5 3 TEXT Virumbrales-Caej_2020.pdf.txt Virumbrales-Caej_2020.pdf.txt Extracted text text/plain 40076 https://riubu.ubu.es/bitstream/10259/5531/4/Virumbrales-Caej_2020.pdf.txt ee3a9098e6c4b0cda89e320b9f62d659 MD5 4 10259/5531 oai:riubu.ubu.es:10259/5531 2021-11-02 13:05:30.195 Repositorio Institucional de la Universidad de Burgos bubrep@ubu.es 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