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Olsson, Sandra K.
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Publications (9 of 9) Show all publications
Olsson, S. (2019). Host-Guest Interactions for Structural Analysis of Organic Molecules: Development of new Tools for Stereochemical Characterization. (Doctoral dissertation). Uppsala: Acta Universitatis Upsaliensis
Open this publication in new window or tab >>Host-Guest Interactions for Structural Analysis of Organic Molecules: Development of new Tools for Stereochemical Characterization
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The focus of this thesis is on the development of molecular tweezers as host-guest systems for stereochemical characterization of small organic molecules.

There are two central problems to stereochemical characterization of small molecules. The first is that there are few methods for the determination of absolute stereochemistry and the complexity of the task increases with the number of chiral centres in the molecule. The second is the flexibility of small molecules. The data received from NMR spectroscopy, the standard method for structural characterization is an average of all conformers present in solution, making exact determination of the structure challenging if stereocenters are involved.

This research group has previously developed two bis-porphyrin molecular tweezers that can be used as hosts for relative stereochemical determination by NMR (NAMFIS) by limiting the flexibility of the guest molecules and for absolute stereochemical determination Exciton-Coupled Circular Dichroism (ECCD) by providing suitable chromophores. However, the use of these tweezers was limited to diamine molecules.

To extend the application of both tweezer host systems, a range of metalloporphyrins have been investigated both computationally and experimentally to identify candidates binding strongly to oxygen containing functional groups (Paper I). One of the porphyrins identified has been used to synthesise a new system with the potential to be used for relative stereochemical determination by NMR (NAMFIS) of molecules with a wide variety of functional groups (Paper IV).

To further develop the systems, the photo-isomerization properties of the stiff stilbene linker of one of the tweezers has been investigated. Macrocyclic diether model compounds, incorporating the stiff stilbene linker have been used to show that the photo-isomerizability strongly is affected by molecular strain (Paper II). The results suggest that if paired with a suitable porphyrin (with no UV/Vis absorption overlap) a photo-switchable tweezer might be constructed.

To map the guest range of the stiff stilbene linked tweezer it was found that this tweezer gives strong to moderate signals for monoamines with a rigid structure (Paper III). As ditopic binding is usually a requirement for an ECCD signal when using bis-porphyrin molecular tweezers, this is a discovery that should be of general interest.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2019. p. 63
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1810
Keywords
metalloporphyrins, host-guest systems, bis-porphyrin tweezers, stiff stilbene macrocycles, organic synthesis, porphyrin binding studies, NMR, ECCD
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-382219 (URN)978-91-513-0660-5 (ISBN)
Public defence
2019-06-14, Room A1:107, BMC, Husargatan 3, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2019-05-22 Created: 2019-04-23 Last updated: 2019-06-18
Olsson, S. K., Dahlstrand, C. & Gogoll, A. (2018). Design of oxophilic metalloporphyrins: an experimental and DFT study of methanol binding. Dalton Transactions, 47(33), 11572-11585
Open this publication in new window or tab >>Design of oxophilic metalloporphyrins: an experimental and DFT study of methanol binding
2018 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 47, no 33, p. 11572-11585Article in journal (Refereed) Published
Abstract [en]

By systematic measurements we have evaluated a series of tetraphenyl metalloporphyrins and halogenated tetraphenyl metalloporphyrin derivatives for binding to ligands with oxygen containing functional groups, using methanol, acetic acid and acetone as examples. Experimental binding constants identified three metalloporphyrins with good binding to all three ligands: MgTPFPP, MgTPPBr8 and ZnTPPBr8 as well as a range of porphyrins binding to select ligands. Based on these results the optimal porphyrins can be selected for the desired binding interactions. We also show how to use DFT calculations to evaluate the potential binding between a metalloporphyrin and a ligand, which is deduced from free energies of binding ΔG, charge transfer ΔQ, and change of metal spin state. Computations on unsubstituted porphyrins in lieu of tetraphenyl porphyrin systems yield reliable predictions of binding interactions with good correlation to the corresponding experimental data. The calculations have also yielded interesting insights into the effect of halogenation in the β-position on the binding to ligands with oxygen containing functional groups.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2018
Keywords
Porphyrins, DFT, host-guest
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-359830 (URN)10.1039/c8dt02432d (DOI)000442509700031 ()30087966 (PubMedID)
Funder
Swedish Research Council, 621-2012-3379Carl Tryggers foundation , 16:156Swedish National Infrastructure for Computing (SNIC), 2018/3-240National Supercomputer Centre (NSC), Sweden, SNIC 2018/3-240
Available from: 2018-09-06 Created: 2018-09-06 Last updated: 2019-04-23Bibliographically approved
Olsson, S. K., Schäfer, C., Blom, M. & Gogoll, A. (2018). Exciton-Coupled Circular Dichroism Characterization of Monotopically Binding Guests in Host-Guest Complexes with a Bis(zinc porphyrin) Tweezer. ChemPlusChem, 83, 1169-1178
Open this publication in new window or tab >>Exciton-Coupled Circular Dichroism Characterization of Monotopically Binding Guests in Host-Guest Complexes with a Bis(zinc porphyrin) Tweezer
2018 (English)In: ChemPlusChem, ISSN 2192-6506, Vol. 83, p. 1169-1178Article in journal (Refereed) Published
Abstract [en]

A stiff-stilbene-linked bisporphyrin tweezer with inherent helicity was used for exciton-coupled circular dichroism (ECCD) characterization of a series of monotopically binding amine guest molecules. CD signals were observed for a variety of monoamines at relatively low tweezer/amine (host/guest) ratios between 1 :10 to 1: 70. For the amines producing the most intense CD signals, a binding stoichiometry of 1:2 was found. A likely explanation is the presence of guest-guest interactions in the complexes. This is supported by the correlation observed between CD signal intensity and magnitude of possible noncovalent binding between the guests, which can be divided into three groups showing no, moderate and strong response, respectively. Further support for this rationalization comes from molecular modelling.

Place, publisher, year, edition, pages
Weinheim: Wiley-VCH Verlagsgesellschaft, 2018
Keywords
bis-porphyrin tweezers, conformation analysis, exciton-coupled circular dichroism, host-guest systems, molecular modeling
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-371629 (URN)10.1002/cplu.201800564 (DOI)000454527200013 ()
Funder
Swedish Research Council, 621-2012-3379Carl Tryggers foundation , CTS 16 : 156
Available from: 2018-12-21 Created: 2018-12-21 Last updated: 2019-04-23Bibliographically approved
Bunrit, A., Watile, R., Dahlstrand, C., Olsson, S., Srifa, P., Huang, G., . . . Samec, J. (2017). H3PO2-catalyzed intramolecular stereospecific nucleophilic substitution of the hydroxyl group in stereogenic alcohols. Paper presented at 254th National Meeting and Exposition of the American-Chemical-Society (ACS) on Chemistry's Impact on the Global Economy, AUG 20-24, 2017, Washington, DC. Abstract of Papers of the American Chemical Society, 254
Open this publication in new window or tab >>H3PO2-catalyzed intramolecular stereospecific nucleophilic substitution of the hydroxyl group in stereogenic alcohols
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2017 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 254Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2017
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-357070 (URN)000429556701849 ()
Conference
254th National Meeting and Exposition of the American-Chemical-Society (ACS) on Chemistry's Impact on the Global Economy, AUG 20-24, 2017, Washington, DC
Available from: 2018-08-13 Created: 2018-08-13 Last updated: 2018-08-13Bibliographically approved
Bunrit, A., Dahlstrand, C., Srifa, P., Olsson, S. K., Huang, G., Biswas, S., . . . Samec, J. S. M. (2016). Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer. Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, 27(2), 173-176
Open this publication in new window or tab >>Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer
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2016 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, Vol. 27, no 2, p. 173-176Article in journal (Refereed) Published
Abstract [en]

A brief overview of the development of direct substitution of the hydroxyl (OH) group of alcohols in our research group is presented. By applying a BrOnsted acid, an intramolecular substitution of the OH group in stereogenic alcohols with chirality transfer was achieved. Noteworthy, the intramolecular substitution has a wide scope in respect to both the nucleophile and also the nucleofuge. A mechanistic study by both experiments and DFT calculations revealed a unique reaction pathway in which the BrOnsted acid operates in a bifunctional manner to promote an S(N)2-type reaction mechanism.

Keywords
green chemistry, BrOnsted acid, base catalysis, chirality transfer, nucleophilic substitutions, asymmetric synthesis, mechanistic studies, DFT calculations
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-276873 (URN)10.1055/s-0035-1560494 (DOI)000368131300004 ()
Funder
Swedish Research CouncilStiftelsen Olle Engkvist ByggmästareWenner-Gren FoundationsGöran Gustafsson Foundation for promotion of scientific research at Uppala University and Royal Institute of TechnologyKnut and Alice Wallenberg Foundation
Available from: 2016-02-16 Created: 2016-02-16 Last updated: 2017-11-30Bibliographically approved
Bunrit, A., Dahlstrand, C., Olsson, S. K., Srifa, P., Huang, G., Orthaber, A., . . . Samec, J. S. M. (2015). Bronsted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer. Journal of the American Chemical Society, 137(14), 4646-4649
Open this publication in new window or tab >>Bronsted Acid-Catalyzed Intramolecular Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer
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2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 14, p. 4646-4649Article in journal (Refereed) Published
Abstract [en]

The hydroxyl group of enantioenriched benzyl, propargyl, allyl, and alkyl alcohols has been intramolecularly displaced by uncharged O-, N-, and S-centered nucleophiles to yield enantioenriched tetrahydrofuran, pyrrolidine, and tetrahydrothiophene derivatives with phosphinic acid catalysis. The five-membered heterocyclic products are generated in good to excellent yields, with high degree of chirality transfer, and water as the only side-product. Racemization experiments show that phosphinic acid does not promote S(N)1 reactivity. Density functional theory calculations corroborate a reaction pathway where the phosphinic acid operates as a bifunctional catalyst in the intramolecular substitution reaction. In this mechanism, the acidic proton of the phosphinic acid protonates the hydroxyl group, enhancing the leaving group ability. Simultaneously, the oxo group of phosphinic acid operates as a base abstracting the nucleophilic proton and thus enhancing the nucleophilicity. This reaction will open up new atom efficient techniques that enable alcohols to be used as nucleofuges in substitution reactions in the future.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-253254 (URN)10.1021/jacs.5b02013 (DOI)000353177100014 ()25803790 (PubMedID)
Available from: 2015-06-12 Created: 2015-05-25 Last updated: 2017-12-04Bibliographically approved
Olsson, S. K., Benito Perez, O., Blom, M. & Gogoll, A.Effect of Ring Size on Photoisomerization Properties of Stiff Stilbene macrocycles.
Open this publication in new window or tab >>Effect of Ring Size on Photoisomerization Properties of Stiff Stilbene macrocycles
(English)Manuscript (preprint) (Other academic)
Abstract [en]

A series of stiff stilbene macrocycles have been studied in order to investigate the possible impact of macrocycle ring size on their photo-dynamic properties. The results show that reducing the ring size counteracts the photoisomerization ability of the macrocycles. However, even the smallest macrocycle studied (stiff stilbene subunits linked by a six carbon chain) showed some degree of isomerization when irradiated. DFT calculations of the energy differences between the E- and Z-isomers show the same trend as the experimental results. Interestingly the DFT study highlights that the energy difference between the E- and Z-isomers of even the largest macrocycle (linked by a twelve carbon chain) is significantly higher than that of the stiff stilbene unit itself. This indicates that a flexible chain may significantly affect the efficiency of photoisomerizations.

Keywords
Stiff stilbene cyclic photoisomerization
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-382215 (URN)
Funder
Swedish Research Council, 621-2012-3379Carl Tryggers foundation , CTS 16:156Swedish National Infrastructure for Computing (SNIC)
Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-04-23
Blom, M., Olsson, S., Norrehed, S., Andersson, C.-H., Grennberg, H. & Gogoll, A.Photomodulable bis-porphyrin molecular tweezers as dynamic host systems for diamine guests.
Open this publication in new window or tab >>Photomodulable bis-porphyrin molecular tweezers as dynamic host systems for diamine guests
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Bisporphyrin molecular tweezers with an enediyne (1) or a stiff stilbene (2) photoswitchable spacer are proposed as systems for modulation of bitopic binding to diamine guests via E/Z photoisomerization. The photoisomerization has been monitored by UV-Vis and 1H NMR spectroscopy and occurs without side reactions such as Bergman cyclization. Possible applications are rationalized in terms of competitive binding involving monoamine/diamine mixtures, and are supported by conformational analysis of the envisioned host-guest complexes. Binding dynamics for conformationally flexible guests show significantly different performance of aliphatic 1,w-diamine guests with varying N-N distance.

Keywords
Bisporphyrin tweezers, supramolecular chemistry, photochemistry
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-267833 (URN)
Funder
Swedish Research Council, 621-2012-3379
Available from: 2015-11-27 Created: 2015-11-27 Last updated: 2016-01-13
Olsson, S. K. & Gogoll, A.Synthesis of a novel bis-Mg-porphyrin tweezer.
Open this publication in new window or tab >>Synthesis of a novel bis-Mg-porphyrin tweezer
(English)Manuscript (preprint) (Other academic)
Abstract [en]

We have synthesised a novel semi-rigid bis-(magnesium-porphyrin) tweezer with a glycoluril backbone. meso-Tetrakis(pentafluorophenyl)porphyrin constitutes the two porphyrin units, each holding a magnesium(II) ion, and being connected to the glycoluril backbone via two -positions. This connection prevents any porphyrin rotation, leaving changes in gap size as sole conformational variation. Magnesium(II) tetrakis(pentafluorophenyl)porphyrin has in previous studies shown to bind well to both nitrogen-containing and oxygen-containing functional groups. The tweezer has the potential to retain this binding ability, which would be useful in the stereochemical characterization of small flexible molecules with multiple stereocentra and a wide variety of functional groups.

Keywords
magnesium-porphyrin tweezer synthesis
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-382217 (URN)
Funder
Swedish Research Council, 621-2012-3379Carl Tryggers foundation , CTS 16:156
Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-04-23
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