Iridium-Catalyzed Isomerization/Bromination of Allylic Alcohols: Synthesis of alpha-Bromocarbonyl Compounds
2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 34, 10703-10709 p.Article in journal (Refereed) Published
alpha-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 alpha-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 alpha-bromoketones and aldehydes in good to excellent yields. The selectivity of the process is determined by the structure of the starting allylic alcohol; thus, alpha-bromoketones formally derived from unsymmetrical ketones can be synthesized in a straightforward and selective manner.
Place, publisher, year, edition, pages
2014. Vol. 20, no 34, 10703-10709 p.
allylic compounds, bromination, iridium, ketones, synthetic methods
IdentifiersURN: urn:nbn:se:su:diva-107423DOI: 10.1002/chem.201402350ISI: 000340505500019OAI: oai:DiVA.org:su-107423DiVA: diva2:748609
FunderKnut and Alice Wallenberg FoundationSwedish Research CouncilVINNOVA