Premium
α‐Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts
Author(s) -
Norrby PerOla,
Petersen Tue B.,
Bielawski Marcin,
Olofsson Berit
Publication year - 2010
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.201001110
Subject(s) - mechanism (biology) , reaction mechanism , chemistry , scheme (mathematics) , computer science , computational chemistry , stereochemistry , philosophy , organic chemistry , catalysis , mathematics , epistemology , mathematical analysis
Surprising equilibration : A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The CI and OI intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final CC bond‐forming step, a [2,3]‐rearrangement from the OI bonded intermediate is slightly preferred over the [1,2]‐elimination from the CI bonded isomer (see scheme).