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Substituent Effects on the Basicity of 3,7-Diazabicyclo[3.3.1]nonanes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Univ Tartu, Inst Chem Phys, EE-51014 Tartu, Estonia .
Univ Tartu, Inst Chem Phys, EE-51014 Tartu, Estonia .
Univ Tartu, Inst Chem Phys, EE-51014 Tartu, Estonia .
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2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 19, 7155-7164 p.Article in journal (Refereed) Published
Abstract [en]

Basicity constants for a series of 3,7-diazabicyclo[3.3.1] nonane derivatives in acetonitrile with a variation over 13 orders of magnitude have been determined using a spectrophotometric titration technique. An excellent correlation between basicity and calculated proton affinities obtained at PCM-B3LYP/6-31+G-(d)//B3LYP/6-31G(d) level was found. The results are discussed in terms of substituent effects and compared to N-15 NMR chemical shifts.

Place, publisher, year, edition, pages
2006. Vol. 71, no 19, 7155-7164 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-94219DOI: 10.1021/jo0604991ISI: 000240371900004OAI: oai:DiVA.org:uu-94219DiVA: diva2:167998
Available from: 2006-04-06 Created: 2006-04-06 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Bispidine Derivatives: Synthesis and Interactions with Lewis Acids
Open this publication in new window or tab >>Bispidine Derivatives: Synthesis and Interactions with Lewis Acids
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, the improved synthesis and investigations into the properties of some 3,7-diazabicyclo[3.3.1]nonane (bispidine) derivatives are described. These compounds are structurally related to the naturally occurring lupanine alkaloids, they are of interest because of their cardiac antiarrhythmic function as well as their use as bases or ligands in organic chemical reactions. Their chemical properties are related to the presence of a rigid molecular scaffold with two nitrogen atoms that can be utilized for binding interactions with a variety of Lewis acids.

An improved synthesis has been developed, providing access to bispidines via bispidinones while avoiding the use of highly toxic hydrazine, which is required as reducing agent in alternative methods.

A series of bispidine derivatives with a variety of substituents were characterized regarding their basicity, which spans thirteen orders of magnitude. Correlations between structure and basicity are discussed and computational methods have been used to propose further derivatives with even higher basicity.

The structures of several bispidine derivatives and their protonated forms have been characterized in the solid state by X-ray crystallography and in solution using NMR spectroscopy. Structure and solution dynamics in a sterically congested (π-allyl)palladium complex with a bispidine ligand have been investigated, revealing mechanistic insight into the dynamic process. Using a bulky bispidine as a temporary ligand for a (η3-propenyl) palladium complex, the novel adamantanoid [{(η3-propenyl)Pd}63-OH)4] cluster was prepared.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2006. 43 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 161
Keyword
Organic chemistry, bispidines, NMR, basicity, structural information, palladium, complexes, Organisk kemi
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-6735 (URN)91-554-6509-9 (ISBN)
Public defence
2006-04-28, Room B22, BMC, Husargatan 3, Uppsala, 13:15
Opponent
Supervisors
Available from: 2006-04-06 Created: 2006-04-06Bibliographically approved

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Ottosson, HenrikGrennberg, HelenaGogoll, Adolf

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