Rhodium-catalysed coupling of allylic, homoallylic, and bishomoallylic alcohols with aldehydes and N-tosylimines: insights into the mechanism
2009 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 351, no 16, 2657-2666 p.Article in journal (Refereed) Published
The isomerisation of alkenols followed by reaction with aldehydes or N-tosylimines catalysed by rhodium complexes has been studied. The catalytically active rhodium complex is formed in situ from commercially available (cyclooctadiene)rhodium(l) chloride dimer [Rh(COD)Cl](2). The tandem process affords aldol and Mannich-type products in excellent yields. The key to the success of the coupling reaction is the activation of the catalysts by reaction with postassium tert-butoxide (t-BuOK), which promotes a catalytic cycle via alkoxides rather than rhodium hydrides. This mechanism minimises the formation of unwanted by-products. The mechanism has been studied by (1)H NMR spectroscopy and deuterium labelling experiments.
Place, publisher, year, edition, pages
2009. Vol. 351, no 16, 2657-2666 p.
aldehydes, allylic alcohols, isomerization, rhodium, N-tosylmines
Research subject Organic Chemistry
IdentifiersURN: urn:nbn:se:su:diva-42169DOI: 10.1002/adsc.200900448ISI: 000272252900022OAI: oai:DiVA.org:su-42169DiVA: diva2:344238