2026-04-29T00:16:23Zhttps://riubu.ubu.es/oai/requestoai:riubu.ubu.es:10259/55312021-11-02T12:05:30Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594
Unlocking the 5‐ exo Pathway with the Au I ‐Catalyzed Alkoxycyclization of 1,3‐Dien‐5‐ynes
Virumbrales, Cintia
Suarez Pantiga, Samuel
Marín Luna, Marta
Silva López, Carlos
Sanz Díez, Roberto
Química orgánica
Chemistry, Organic
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 eInnovacinand FEDER (CTQ2016-75023-C2-1-P and 2-P), Junta de Castilla yLenand FEDER (BU291P18) and Xunta de Galiza (ED431C2017/70and ED431E 2018/07)
2020-10-29T10:46:57Z
2020-10-29T10:46:57Z
2020-07
info:eu-repo/semantics/article
info:eu-repo/semantics/submittedVersion
0947-6539
http://hdl.handle.net/10259/5531
10.1002/chem.202001296
1521-3765
eng
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
info:eu-repo/semantics/openAccess
application/pdf
Wiley