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Efficient Route to the Pineal Hormone Melatonin by Radical-Based Indole Synthesis
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry.
2003 (English)In: Synthetic Communications, ISSN 0039-7911, E-ISSN 1532-2432, Vol. 33, no 20, 3631-3641 p.Article in journal (Refereed) Published
Abstract [en]

The hormone melatonin, which is known to have a range of important biological effects, has been prepared in a high-yielding route that features formation of the indole nucleus by radical cyclization. Mediation of the radical cyclization by tristrimethylsilylsilane (TTMSS) is more efficient than by N-ethylpiperidine hypophosphite.

Place, publisher, year, edition, pages
2003. Vol. 33, no 20, 3631-3641 p.
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-90419DOI: 10.1081/SCC-120024751OAI: oai:DiVA.org:uu-90419DiVA: diva2:162768
Available from: 2003-05-12 Created: 2003-05-12 Last updated: 2013-06-13Bibliographically approved
In thesis
1. Construction of Five-Membered Heterocyclic Compounds via Radical Cyclization
Open this publication in new window or tab >>Construction of Five-Membered Heterocyclic Compounds via Radical Cyclization
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes how radical cyclization chemistry can be applied for the construction of heterocyclic compounds.

In the first part, a series of electron deficient α-phenylselenenylalkenes were prepared via a PhSeCl-addition/HCl-elimination sequence. Allyl- and propargylamines readily underwent conjugate addition to these species to produce pyrrolidines or dihydropyrrol derivatives, after triethylborane initiated reductive radical cyclization in the presence of tris(trimethylsilyl)silane.

The second part describes a convergent synthesis of the pineal hormone melatonin. The indole nucleus is secured via a tris(trimethylsilyl)silane mediated 5-exo radical cyclization. The protocol provides convenient and simple access to compounds useful for studies of biological activity and structure activity relationships.

The third part describes construction of substituted tetrahydrofuran-3-ones and pyrrolidin-3-ones. Regioselective ring-opening of epoxides or aziridines with benzeneselenolate/tellurolate, followed by Michael addition to electron deficient alkynes afforded the corresponding O/N-vinylated compounds. The tetrahydrofuran-3-ones and pyrrolidin-3-ones were secured via radical carbonylation/reductive cyclization using pressurized carbon monoxide (80 atm).

The fourth part is concerned with the effect of an N-protecting group on the cyclization of 2-substituted-3-aza-5-hexenyl radicals. Relative energies for reactants and transition states were determined using density functional calculations. Reactant and transition state conformers leading to cis-product were lower in energy than those leading to trans-product. The results can be explained by the unfavorable 1,2-strain present in chair-equatorial and boat-equatorial conformers.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2003. 59 p.
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1104-232X ; 845
Organic chemistry, radical, cyclization, carbonylation, melatonin, pyrrolidine, pyrrolidin-3-one, tetrahydrofuran-3-one, Organisk kemi
National Category
Organic Chemistry
Research subject
Organic Chemistry
urn:nbn:se:uu:diva-3429 (URN)91-554-5648-0 (ISBN)
Public defence
2003-06-04, B42, BMC, Uppsala, 10:15
Available from: 2003-05-12 Created: 2003-05-12Bibliographically approved

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