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Synthesis of Tetrahydrofuran and Pyrrolidine Derivatives Utilising Radical Reactions: Organochalcogenides in Reductive, Carbonylative and Group-Transfer Cyclisation
Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes free-radical reactions for the construction of tetrahydrofuran and pyrrolidine derivatives. The studies are concerned with (i) diastereoselectivity in radical cyclisation, (ii) construction of tetrahydrofuran-3-ones and pyrrolidin-3-ones via radical carbonylation/cyclisation and (iii) synthesis of tetrahydrofuran derivatives via group-transfer cyclisation of organochalcogen compounds.

(i) Diastereoselectivity in the synthesis of tetrahydrofuran derivatives via radical cyclisation was controlled by addition of Lewis acids. In the synthesis of 2,4-disubstitued tetrahydrofurans, the trans-isomer was formed as the major product in the unperturbed reaction. Upon addition of trialkylalumiums the diastereoselectivity was reversed. In a similar fashion, exo/endo-diastereoselectivity in the synthesis of bicyclic 2,3,4-trisubstituted tetrahydrofurans could also be controlled.

(ii) Procedures for construction of tetrahydrofuran-3-ones and pyrrolidin-3-ones were presented. Epoxides were ring-opened with benzeneselenolate or benzenetellurolate and the resulting β-hydroxyalkyl phenyl chalcogenides were vinylated using ethyl propiolate/NMM or E-1,2-bis(phenylsulfonyl)ethylene/NaH. The corresponding nitrogen analogues were accessed by N-vinylation of aziridines followed by benzeneselenolate ring-opening. The two types of organochalcogen radical precursors were then treated with TTMSS/AIBN under an atmosphere of carbon monoxide (80 atm) to afford tetrahydrofuran-3-ones and pyrrolidin-3-ones, respectively, in high yields.

(iii) Microwaves were found to induce group-transfer cyclisation of β-allyloxyalkyl aryl chalcogenides. Short time heating (3-10 min) at 250 oC in ethylene glycol was required to obtain tetrahydrofuran derivatives in 60-91% yield.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2004. , p. 46
Series
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1104-232X ; 946
Keyword [en]
Organic chemistry
Keyword [sv]
Organisk kemi
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-4018ISBN: 91-554-5893-9 (print)OAI: oai:DiVA.org:uu-4018DiVA, id: diva2:164165
Public defence
2004-03-18, B42, BMC, Uppsala, 10:15
Opponent
Supervisors
Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
List of papers
1. Diastereocontrol by Trialkylaluminums in the Synthesis of Tetrahydrofurans via Radical Cyclisation
Open this publication in new window or tab >>Diastereocontrol by Trialkylaluminums in the Synthesis of Tetrahydrofurans via Radical Cyclisation
2001 In: Organic Letters, Vol. 3, p. 3459-Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-91437 (URN)
Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
2. Construction of Tetrahydrofuran-3-ones from Readily Available Organochalcogen Precursors via Radical Carbonylation/Reductive Cyclization
Open this publication in new window or tab >>Construction of Tetrahydrofuran-3-ones from Readily Available Organochalcogen Precursors via Radical Carbonylation/Reductive Cyclization
2002 In: Organic Letters, Vol. 4, p. 3-Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-91438 (URN)
Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
3. Radical Carbonylation/Reductive Cyclization for the Construction of Tetrahydrofuran-3-ones and Pyrrolidin-3-ones
Open this publication in new window or tab >>Radical Carbonylation/Reductive Cyclization for the Construction of Tetrahydrofuran-3-ones and Pyrrolidin-3-ones
2003 In: Journal of Organic Chemistry, Vol. 68, p. 8386-Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-91439 (URN)
Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved
4. Microwave-Assisted Group-Transfer Cyclisation of Organotellurium Compounds
Open this publication in new window or tab >>Microwave-Assisted Group-Transfer Cyclisation of Organotellurium Compounds
Article in journal (Refereed) Submitted
Identifiers
urn:nbn:se:uu:diva-91440 (URN)
Available from: 2004-02-26 Created: 2004-02-26Bibliographically approved

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