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Virumbrales, Cintia Suarez Pantiga, Samuel Marín Luna, Marta Silva López, Carlos Sanz Díez, Roberto 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