Theoretical Mechanistic Study of the TBD-Catalyzed Intramolecular Aldol Reaction of Ketoaldehydes
2010 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 75, no 14, 4728-4736 p.Article in journal (Refereed) Published
The intramolecular aldol reaction of acyclic ketoaldehydes catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is investigated using density functional theory calculations. Compared to the aldol reaction catalyzed by proline, the use of TBD provides a unique and unusual complete switch of product selectivity. Three mechanistic pathways are proposed and evaluated. In the favored mechanism TBD catalyzes the reaction through proton transfer in two steps, enolization and C-C bond formation. The computationally predicted stereochemical outcome of the reaction is in agreement with experimental findings. Additionally, these studies provide new insights into the activation mode of bifunctional guanidine catalysts in aldol reactions.
Place, publisher, year, edition, pages
2010. Vol. 75, no 14, 4728-4736 p.
RING-OPENING POLYMERIZATION, DENSITY-FUNCTIONAL THEORY, ASYMMETRIC ORGANOCATALYSIS, CYCLIC ESTERS, ENANTIOSELECTIVE ORGANOCATALYSIS, PROLINE, WATER, GUANIDINE, ACETALDEHYDE, ALDEHYDES
IdentifiersURN: urn:nbn:se:kth:diva-11613DOI: 10.1021/jo100488gISI: 000279569500007ScopusID: 2-s2.0-77954554809OAI: oai:DiVA.org:kth-11613DiVA: diva2:278332
FunderSwedish Research Council
Uppdaterad från manuskift 20100719
QC 201007192009-11-252009-11-252011-02-02Bibliographically approved