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Nature of the Intermediates in Gold(I)‐Catalyzed Cyclizations of 1,5‐Enynes
Author(s) -
LópezCarrillo Verónica,
Huguet Núria,
Mosquera Ángeles,
Echavarren Antonio M.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101749
Subject(s) - cycloisomerization , carbene , catalysis , chemistry , photochemistry , medicinal chemistry , organic chemistry
The carbene or carbocationic nature of the intermediates in the gold‐catalyzed cycloisomerization of 1,5‐enynes can be revealed, depending on the ligands on the gold catalysts. Gold complexes with highly electron‐donating ligands promote reactions that proceed via intermediates with carbene‐like character, leading to products with a bicyclo[3.1.0]hexene skeleton. The intermediate cyclopropyl endo ‐gold carbenes formed in this cyclization have been trapped, for the first time, to give biscyclopropane derivatives in a reaction that proceeds in a concerted fashion, according to DFT calculations.