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Palladium(II)-Catalyzed Reactions of Allenes with Lithium Bromide and Cyclization of α-Amino Allenes to Pyrrolines
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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.
Keyword [en]
Palladium, allene, pyrroline, palladium(II)-catalysis
Identifiers
URN: urn:nbn:se:su:diva-70ISBN: 91-7265-820-7 (print)OAI: oai:DiVA.org:su-70DiVA: diva2:197448
Public defence
2004-03-31, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
List of papers
1. Intramolecular Palladium(II)-Catalyzed 1,2-Addition to Allenes
Open this publication in new window or tab >>Intramolecular Palladium(II)-Catalyzed 1,2-Addition to Allenes
2000 In: Journal of the American Chemical Society, ISSN 0002-7863, Vol. 122, no 40, 9600-9609 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24397 (URN)
Note
Part of urn:nbn:se:su:diva-70Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
2. Palladium(II)-Catalyzed SN2' Reactions of α-Allenic Acetates: Stereoconvergent Synthesis of (Z,E)-2-Bromo-1,3-dienes
Open this publication in new window or tab >>Palladium(II)-Catalyzed SN2' Reactions of α-Allenic Acetates: Stereoconvergent Synthesis of (Z,E)-2-Bromo-1,3-dienes
2001 In: Journal of Organic Chemistry, Vol. 66, no 24, 8120-8126 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24398 (URN)
Note
Part of urn:nbn:se:su:diva-70Available from: 2004-03-11 Created: 2004-03-11Bibliographically approved
3. Mild and Efficient Palladium(II)-Catalyzed Racemization of Allenes
Open this publication in new window or tab >>Mild and Efficient Palladium(II)-Catalyzed Racemization of Allenes
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
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24399 (URN)10.1039/B316482A (DOI)
Note
Part of urn:nbn:se:su:diva-70Available from: 2004-03-11 Created: 2004-03-11 Last updated: 2017-12-13Bibliographically approved
4. Simple, Enantiocontrolled Synthesis of 3-Pyrrolines from α-Amino Allenes
Open this publication in new window or tab >>Simple, Enantiocontrolled Synthesis of 3-Pyrrolines from α-Amino Allenes
2004 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, Vol. 2004, no 15, 3240-3243 p.Article in journal (Refereed) Published
Abstract [en]

Cyclization of -amino allenes in the presence of N-bromosuccinimide afforded pyrrolines in good yields. The products were obtained with high enantiomeric excesses when optically active allenes were used as substrates. The synthesis of a 2,5-dehydroprolinol derivative is also presented.

Place, publisher, year, edition, pages
wiley, 2004
Keyword
Allenes;Cyclization;Nitrogen heterocycles
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24400 (URN)10.1002/ejoc.200400211 (DOI)
Note
Part of urn:nbn:se:su:diva-70Available from: 2004-03-11 Created: 2004-03-11 Last updated: 2017-12-13Bibliographically approved

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