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Divergent Gold‐Catalyzed Rearrangement of 1‐Alkenyl‐2‐alkynylcyclopropanes: Enyne Transformation Controlled by a Silicon Moiety
Author(s) -
González Jairo,
Allegue Darío,
Fernández Sergio,
Rodríguez Miguel A.,
Santamaría Javier,
Ballesteros Alfredo
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000521
Subject(s) - chemistry , isomerization , allylic rearrangement , intramolecular force , carbene , moiety , silylation , catalysis , enyne , photochemistry , rearrangement reaction , allene , silanes , medicinal chemistry , stereochemistry , organic chemistry , silane
Here we report a gold(I)‐catalyzed rearrangement for a special type of alkynylcyclopropanes, such as (6‐ethynylbicyclo[3.1.0]hex‐2‐en‐6‐yl)silanes. These enynes evolved through an isomerization reaction towards the formation of isomeric alkynylcyclopropanes instead of the expected alkynylcyclohexadienes. A computational study on the reaction mechanism revealed the participation of a polycyclic gold(I) carbene complex as intermediate instead of a σ‐allylic gold cation which is in agreement with the expected influence in the energy of those intermediates due to the presence of the silyl group. Finally, this gold(I) carbene intermediate could be experimentally intercepted through intramolecular cyclopropanations.