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Selective Synthesis of Unsymmetrical Aliphatic Acyloins through Oxidation of Iridium Enolates
Author(s) -
SanzMarco Amparo,
MartinezErro Samuel,
MartínMatute Belén
Publication year - 2018
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.201803117
Subject(s) - allylic rearrangement , iridium , ketone , hydride , chemistry , surface modification , combinatorial chemistry , catalysis , alcohol oxidation , organic chemistry , metal
The first method to access unsymmetrical aliphatic acyloins is presented. The method relies on a fast 1,3‐hydride shift mediated by an Ir III complex in allylic alcohols followed by oxidation with TEMPO + . The direct conversion of allylic alcohols into acyloins is achieved in a one‐pot procedure. Further functionalization of the Cα′ of the α‐amino‐oxylated ketone products gives access to highly functionalized unsymmetrical aliphatic ketones, which further highlights the utility of this transformation.