Publications by authors named "Bret R Van Ausdall"

2 Publications

  • Page 1 of 1

Imidazolidene carboxylate bound MBPh4 complexes (M = Li, Na) and their relevance in transcarboxylation reactions.

J Org Chem 2011 Oct 27;76(20):8413-20. Epub 2011 Sep 27.

Department of Chemistry, Henry Eyring Building, University of Utah, 315 S. 1400 E, Salt Lake City, Utah 84112-0850, United States.

Combination of 1,3-bis(2,6-diisopropylphenyl)imidazolum-2-carboxylate (IPrCO(2)) with the Lewis acids MBPh(4), where M = Li or Na, provided two separate complexes. The crystal structures of these complexes revealed that coordination to NaBPh(4) yielded a dimeric species, yet coordination of IPrCO(2) with LiBPh(4) yielded a monomeric species. Combination of 1,3-bis(2,4,6-trimethylphenyl)imidazolum-2-carboxylate (IMesCO(2)) with LiBPh(4) also afforded a dimeric species that was similar in global structure to that of the IPrCO(2)+NaBPh(4) dimer. In all three cases, the cation of the organic salt was coordinated to the oxyanion of the zwitterionic carboxylate. Thermogravimetric analysis of the crystals demonstrated that decarboxylation occurred at lower temperatures than the decarboxylation temperature of the parent NHC·CO(2) (NHC = N-heterocyclic carbene). Kinetic analysis of the transcarboxylation of IPrCO(2) to acetophenone with NaBPh(4) to yield sodium benzoylacetate was performed. First-order dependences were observed for IPrCO(2) and acetophenone, whereas zero -order dependence was observed for NaBPh(4). Direct dicarboxylation was observed when I(t)BuCO(2) was added to MeCN in the absence of added MBPh(4).
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http://dx.doi.org/10.1021/jo201647bDOI Listing
October 2011

A systematic investigation of factors influencing the decarboxylation of imidazolium carboxylates.

J Org Chem 2009 Oct;74(20):7935-42

Department of Chemistry, Henry Eyring Building, University of Utah, 315 S. 1400 East, Salt Lake City, Utah 84112-0850, USA.

A series of 1,3-disubstituted-2-imidazolium carboxylates, an adduct of CO(2) and N-heterocyclic carbenes, were synthesized and characterized using single crystal X-ray, thermogravimetric, IR, and NMR analysis. The TGA analysis of the NHC-CO(2)'s shows that as steric bulk on the N-substituent increases, the ability of the NHC-CO(2) to decarboxylate increases. The comparison of NHC-CO(2)'s with and without methyls at the 4,5-position indicate that extra electron density in the imidazolium ring enhances the stability of an NHC-CO(2) thereby making it less prone to decarboxylation. Single crystal X-ray analysis shows that the torsional angle of the carboxylate group and the C-CO(2) bond length with respect to the imidazolium ring is dependent on the steric bulk of the N-substituent. Rotamers in the unit cell of a single crystal of I(t)BuPrCO(2) (2f) indicate that the C-CO(2) bond length increases as the N-substituents rotate toward the carboxylate moiety, which suggests that rotation of the N-substituents through the plane of the C-CO(2) bond may be involved in the bond breaking event to release CO(2).
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http://dx.doi.org/10.1021/jo901791kDOI Listing
October 2009
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