RT info:eu-repo/semantics/article
T1 Unlocking the 5‐            exo            Pathway with the Au            I            ‐Catalyzed Alkoxycyclization of 1,3‐Dien‐5‐ynes
A1 Virumbrales Ortiz, Cintia
A1 Suarez Pantiga, Samuel
A1 Marín Luna, Marta
A1 Silva López, Carlos
A1 Sanz Díez, Roberto
K1 Química orgánica
K1 Chemistry, Organic
AB 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.
PB Wiley
SN 0947-6539
YR 2020
FD 2020-07
LK http://hdl.handle.net/10259/5531
UL http://hdl.handle.net/10259/5531
LA eng
NO 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)
DS Repositorio Institucional de la Universidad de Burgos
RD 17-abr-2024