Directing the regioselectivity of rhodium(I) catalysed cyclisation of 2-alkynyl benzoic acids

Bradley Y W Man, Astrid Knuhtsen, Michael J. Page, Barbara A. Messerle*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)


Rhodium(I) dicarbonyl complexes 1-4 containing chelating N-donor ligands bis(pyrazolyl)methane (bpm), bis(imidazolyl)methane (bim), tris(pyrazolyl) toluidine (tpt) or tris(imidazolyl)methanol (tim) were investigated as catalysts for the hydroalkoxylation of alkynyl benzoic acids (5a-g). The regioselectivity of the reaction was shown to be highly dependent on the nature of the terminal alkyne substituent (R) of the alkynol substrate. It was also determined that the presence of a third uncoordinated N-donor group in complexes 3 and 4 suppressed the catalytic efficiency of these complexes, and that the selectivity of the reaction for forming either endocyclic (6) or exocyclic (7) hydroalkoxylation products was influenced by the pendant hydroxyl group present in complex 4. We used 13C NMR spectroscopy to quantify the polarity of the alkynyl benzoic acid C≡C bond and our efforts to correlate this measure of bond polarity to the observed regioselectivity of the reaction are discussed.

Original languageEnglish
Pages (from-to)248-252
Number of pages5
Publication statusPublished - 2013
Externally publishedYes


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