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Iridium‐Catalyzed Isomerization/Bromination of Allylic Alcohols: Synthesis of α‐Bromocarbonyl Compounds
Author(s) -
Gómez Antonio Bermejo,
Erbing Elis,
Batuecas María,
VázquezRomero Ana,
MartínMatute Belén
Publication year - 2014
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.201402350
Subject(s) - allylic rearrangement , electrophile , halogenation , isomerization , chemistry , selectivity , iridium , catalysis , organic chemistry , alcohol , combinatorial chemistry
Abstract α‐Brominated ketones and aldehydes, with two adjacent electrophilic carbon atoms, are highly valuable synthetic intermediates in organic synthesis, however, their synthesis from unsymmetrical ketones is very challenging, and current methods suffer from low selectivity. We present a new, reliable, and efficient method for the synthesis of α‐bromocarbonyl compounds in excellent yields and with excellent selectivities. Starting from allylic alcohols as the carbonyl precursors, the combination of a 1,3‐hydrogen shift catalyzed by iridium(III) with an electrophilic bromination gives α‐bromoketones and aldehydes in good to excellent yields. The selectivity of the process is determined by the structure of the starting allylic alcohol; thus, α‐bromoketones formally derived from unsymmetrical ketones can be synthesized in a straightforward and selective manner.