Iridium-catalyzed isomerization/bromination of allylic alcohols: synthesis of α-bromocarbonyl compounds.
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.
Department of Organic Chemistry and Berzelii Center EXSELENT, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden. Fax: (+) 46815 49 08; Berzelii Center EXSELENT on Porous Materials, Stockholm University, SE-106 91 Stockholm, Sweden.
Antonio
A
Bermejo Gómez
Elis
E
Erbing
María
M
Batuecas
Ana
A
Vázquez-Romero
Belén
B
Martín-Matute
allylic compounds; bromination; iridium; ketones; synthetic methods