Change search
ReferencesLink to record
Permanent link

Direct link
Mild and Efficient Palladium(II)-Catalyzed Racemization of Allenes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2004 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 8, 964-965 p.Article in journal (Refereed) Submitted
Abstract [en]

Allenes undergo racemization in the presence of catalytic amounts of Pd(OAc)2/LiBr under mild conditions; the reaction proceeds via a bromopalladation–debromopalladation sequence and tolerates various functional groups.


Place, publisher, year, edition, pages
Royal Society of Chemistry , 2004. no 8, 964-965 p.
National Category
Organic Chemistry
URN: urn:nbn:se:su:diva-24399DOI: 10.1039/B316482AOAI: diva2:197446
Part of urn:nbn:se:su:diva-70Available from: 2004-03-11 Created: 2004-03-11 Last updated: 2010-12-08Bibliographically approved
In thesis
1. Palladium(II)-Catalyzed Reactions of Allenes with Lithium Bromide and Cyclization of α-Amino Allenes to Pyrrolines
Open this publication in new window or tab >>Palladium(II)-Catalyzed Reactions of Allenes with Lithium Bromide and Cyclization of α-Amino Allenes to Pyrrolines
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based on three novel palladium(II)-catalyzed reactions of allenes with lithium bromide and a bromonium ion induced cyclization of allenyl amides to pyrrolines. In Paper I a 1,2-functionalization of allenes is presented where bromide adds as a first nucleophile followed by intramolecular attack by an oxygen or nitrogen nucleophile. Chapter 2 deals with the extension of this reaction to different nitrogen nucleophiles such as urea, carbamate, and N-tosyl carbamate providing access to substituted pyrrolidines and oxazolidines in good yields under mild reaction conditions.

Paper II deals with a stereoconvergent, palladium(II)-catalyzed SN2’ reaction of α-acetoxy allenes with bromide as nucleophile. In this reaction substituted (Z,E)-2-bromo-1,3-dienes are produced in good yields with excellent diastereo-selectivity.

Paper III describes a mild racemization reaction of chiral allenes. The effect of the functional group present in the molecule on the reaction rate is examined. All these reactions published in Papers I-III proceed through a common intermediate: a 2-bromo-(π-allyl)palladium complex.

The fourth paper describes a simple, efficient, and enantiocontrolled cyclization of N-protected α-allenyl amines with N-bromosuccinimide (NBS) to afford 3-bromo-pyrrolines. The synthesis of optically active 2,5-dehydroprolinol derivative is also described. The mechanism, scope, and limitations of all four reactions are discussed in this thesis.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2004. 44 p.
Palladium, allene, pyrroline, palladium(II)-catalysis
urn:nbn:se:su:diva-70 (URN)91-7265-820-7 (ISBN)
Public defence
2004-03-31, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Bäckvall, Jan-Erling
By organisation
Department of Organic Chemistry
In the same journal
Chemical Communications
Organic Chemistry

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: 41 hits
ReferencesLink to record
Permanent link

Direct link