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Gold‐Catalyzed 1,2‐/1,2‐Bis‐acetoxy Migration of 1,4‐Bis‐propargyl Acetates: A Mechanistic Study
Author(s) -
de Haro Teresa,
GómezBengoa Enrique,
Cribiú Riccardo,
Huang Xiaogen,
Nevado Cristina
Publication year - 2012
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.201103472
Subject(s) - propargyl , catalysis , chemistry , medicinal chemistry , organic chemistry
The late transition metal catalyzed rearrangement of propargyl acetates offers an interesting platform for the development of synthetically useful transformations. We have recently shown that gold complexes can catalyze a highly selective tandem 1,2‐/1,2‐bis‐acetoxy migration in 1,4‐bis‐propargyl acetates to form 2,3‐bis‐acetoxy‐1,3‐dienes. In this way, (1 Z ,3 Z )‐ or (1 Z ,3 E )‐ and (1 E ,3 Z )‐1,3‐dienes could be obtained in a stereocontrolled manner depending on the electronic and steric features of the ancillary ligand bound to gold and the substituents at the propargylic positions. In this work, we report an experimental study on the scope of this transformation, plus a detailed theoretical examination of the reaction mechanism, which has revealed the key features responsible for the reaction stereoselectivity. Synthetic applications towards the one‐pot synthesis of quinoxaline heterocycles and tandem Diels–Alder processes have also been devised.