Change search
ReferencesLink to record
Permanent link

Direct link
Structure-Reactivity Relationship Studies for Guanidine-Organocatalyzed Direct Intramolecular Aldolization of Ketoaldehydes
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
Show others and affiliations
2010 (English)In: CHEMCATCHEM, ISSN 1867-3880, Vol. 2, no 12, 1573-1581 p.Article in journal (Refereed) Published
Abstract [en]

Structure-reactivity studies are performed to explore the reaction mechanism of the guanidine-catalyzed intramolecular aldol reaction of ketoaldehydes. A large number of guanidine and guanidine-like catalysts are synthesized and their properties studied. Kinetic profiles and pK(a) values of the catalysts are measured and correlated to reaction barriers calculated using density functional theory (DFT). The DFT calculations show that structural rigidity influences the pKa of the guanidines. Although the basicity is a very important factor in the catalysis, it is not sufficient to fully account for its catalytic efficiency. The availability of two aligned nitrogen reaction sites for proton shuttling in the transition state is an essential feature that helps to rationalize the reactivity pattern and the activation mode for this family of organocatalysts.

Place, publisher, year, edition, pages
2010. Vol. 2, no 12, 1573-1581 p.
Keyword [en]
aldolization, density functional calculations, organocatalysis, regioselectivity, structure-activity relationships
National Category
Biochemistry and Molecular Biology
URN: urn:nbn:se:kth:diva-27689DOI: 10.1002/cctc.201000227ISI: 000284717800014ScopusID: 2-s2.0-79957884399OAI: diva2:380290
Swedish Research Council
QC 20101221Available from: 2010-12-21 Created: 2010-12-20 Last updated: 2010-12-21Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Hammar, Peter
By organisation
Theoretical Chemistry
Biochemistry and Molecular Biology

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 23 hits
ReferencesLink to record
Permanent link

Direct link