Premium
1,3‐Li/H Shift of 1‐Aryl‐1,2‐alkadienyl Reagents: An Experimental and Theoretical Study
Author(s) -
Alouane Nacira,
Bentayeb Kamel,
Vrancken Emmanuel,
Gérard Hélène,
Mangeney Pierre
Publication year - 2008
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.200801849
Subject(s) - aryl , reagent , proton , lithium (medication) , allene , chemistry , computational chemistry , reaction mechanism , mechanism (biology) , combinatorial chemistry , medicinal chemistry , organic chemistry , catalysis , physics , nuclear physics , medicine , alkyl , quantum mechanics , endocrinology
A‐Li shuffle : Experimental and computational data are employed to elucidate the mechanistic aspects of the 1,3‐lithium shift occurring in the allenyllithium complexes derived from 1‐aryl‐1‐alkynes. A central role is shown to be played by proton donors, resulting in the in situ formation of a transient allene. This highlights the role of water in the reaction mechanism and explains the disconcerting non‐reproducibility of “proton‐free” reaction procedures.