Rhodium(I)-catalysed intramolecular [2+2+2] cyclotrimerisations of 15-, 20- and 25-membered azamacrocycles: Experimental and theoretical mechanistic studies

Anna Dachs, Anna Torrent, Anna Roglans, Teodor Parella, Sílvia Osuna, Miquel Solà

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43 Citations (Scopus)

Abstract

A new series of 20- and 25- membered polyacetylenic azamacrocy- cles have been satisfactorily prepared and completely characterised by spec- troscopic methods. Various [2+2+2] cy- clotrimerisation processes catalysed by the Wilkinson's catalyst, [RhCl- (PPh3)3], were tested in the above- mentioned macrocycles. The 25-membered azamacrocycle (like the previously synthesised 15-membered azama- crocyle) led to the expected cyclotri-merised compound in contrast to the 20-membered macrocycle, which is characterised by its lack of reactivity. The difference in reactivity of the 15-, 20- and 25-membered macrocycles has been rationalised through density functional theory calculations.
Original languageEnglish
Pages (from-to)5289-5300
JournalChemistry - A European Journal
Volume15
Issue number21
DOIs
Publication statusPublished - 18 May 2009

Keywords

  • Cyclotrimerization
  • Density functional calculations
  • Macrocycles
  • Reaction mechanisms
  • Rhodium

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