uu.seUppsala University Publications
Change search
ReferencesLink to record
Permanent link

Direct link
Catalytic asymmetric chiral lithium amide-promoted epoxide rearrangement: a NMR spectroscopic and kinetic investigation
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry, Organic Chemistry. (Peter Dinér)
2010 (English)In: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 21, no 21-22, 2733-2739 p.Article in journal (Refereed) Published
Abstract [en]

The lithium amide derived from the chiral diamine (1R,3S,4S)-3-(1-pyrrolidinyl)methyl-2-azabicyclo[2.2.1]heptane, has been reported to catalytically deprotonate cyclohexene oxide and other epoxides, yielding chiral allylic alcohols in excellent enantiomeric excess. In this work, 6Li, 1H and 13 C NMR spectroscopy have been used to study the aggregation of the chiral lithium amide in THF and the influence on the aggregation by the addition of additives, such as 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU). The activated complex under catalytic deprotonation of cyclohexene oxide, that is, with excess Li-DBU and free DBU, is built from one monomer of the chiral lithium amide, one molecule of epoxide and one additional molecule of DBU. The reaction order (0.97) obtained for the bulk base Li-DBU shows an inverse dependence on the concentration, suggesting a deaggregation of the initial mixed dimer to a monomer-based transition state containing a monomer of the lithium amide.

Place, publisher, year, edition, pages
2010. Vol. 21, no 21-22, 2733-2739 p.
National Category
Other Basic Medicine
URN: urn:nbn:se:uu:diva-137505DOI: 10.1016/j.tetasy.2010.10.034ISI: 000285951200021OAI: oai:DiVA.org:uu-137505DiVA: diva2:378406
internal-pdf://science-7-2000962304/science-7.pdfAvailable from: 2010-12-15 Created: 2010-12-15 Last updated: 2011-12-02Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Dinér, Peter
By organisation
Organic Chemistry
In the same journal
Tetrahedron: asymmetry
Other Basic Medicine

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: 184 hits
ReferencesLink to record
Permanent link

Direct link