Oxazol-2-ylidenes. A new class of stable carbenes?

Zsolt Kelemen, Oldamur Hollóczki, Julianna Oláh, László Nyulászi

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21 Citations (Scopus)

Abstract

The investigation of the stability of several imidazol-2-ylidene analogue cyclic carbenes by an isodesmic reaction has revealed that the hitherto unknown oxazol-2-ylidene exhibits only slightly smaller stability than imidazol-2-ylidene, outperforming some of the already synthesized carbenes. Selenazol-2-ylidene also shows significant stability. The contribution of aromaticity to the stabilization has been analysed for the different five-membered ring carbenes, and was found to be relatively small for the oxygen containing systems. Investigation of possible reactivity/decomposition pathways reveals that properly substituted oxazol-2-ylidene is stable against dimerization. The thermodynamically feasible cycloreversion reaction yielding isocyanate and acetylene is prevented by a significant barrier, and furthermore with proper substitution (ring annellation) the ring can be stabilized thermodynamically as well. While in the presence of water a hydrolytic ring opening occurs; this reaction can be hindered if the water content of the reaction mixture is reduced to a few equivalents. This hydrolytic behaviour as well as the electrophilicity and nucleophilicity indices of several known nucleophilic carbenes were compared, revealing that oxazol-2-ylidene exhibits a reduced nucleophilicity with respect to imidazol-2-ylidene, while its electrophilicity is only slightly increased. This unique combination might result in unexpected (organo)catalytic activities, further expanding the colourful applications of NHCs.

Original languageEnglish
Pages (from-to)7970-7978
Number of pages9
JournalRSC Advances
Volume3
Issue number21
DOIs
Publication statusPublished - Jun 7 2013

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ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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