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Mechanistic Studies on the Rearrangement of 1‐Alkenyl‐2‐alkynylcyclopropanes: From Allylic Gold(I) Cations to Stable Carbocations
Author(s) -
Tudela Eva,
González Jairo,
Vicente Rubén,
Santamaría Javier,
Rodríguez Miguel A.,
Ballesteros Alfredo
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201407055
Subject(s) - carbocation , allylic rearrangement , chemistry , nuclear magnetic resonance spectroscopy , affinities , spectroscopy , photochemistry , stereochemistry , crystallography , computational chemistry , catalysis , organic chemistry , physics , quantum mechanics
An allylic gold(I) cation, proposed as key intermediate in the gold‐promoted rearrangement of 1,5‐enynes bearing a fixed conformation, has been detected and characterized by NMR spectroscopy. Moreover, its participation in the overall transformation was confirmed. Computational studies indicate that the gold‐catalyzed transformation occurs through an uncommon rearrangement. Additionally, this study led us to isolate and characterize a stable homoantiaromatic carbocation.