CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Bifunctionalization of Small Organic Molecules Based on Fluorine Incorporation
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-7276-2755
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The dissertation work that is summarized in this thesis describes novel syntheses of organofluorine compounds with a broad coverage of different fluorine-containing motifs.

Chapter 2.1 covers works on the exploration of new trifluoromethylthiolating reactions of diazocarbonyl compounds. A rhodium-catalyzed oxy-trifluoromethylthiolation reaction enabled the synthesis of densely functionalized carbonyl compounds. Different oxygen nucleophiles, for instance alcohols, ethers and acetals underwent this transformation.

A zinc triflimide mediated three-component reaction established an arylation-trifluoromethylthiolation of diazocarbonyl compounds. In situ generation of triarylboranes was rendered most effective for the arylation event. Both procedures made use of the high reactivity of a recently developed electrophilic trifluoromethylthiolating reagent.

The second chapter (2.2) is dedicated to the late-stage construction of trifluoromethyl motifs. By means of halide exchange, nucleophilic fluoride from a copper(I)-complex could be used to exchange bromide with fluoride in the α-position to carbonyl groups as well as in benzylic positions.

The third chapter (2.3) covers the development of an enantioselective fluorocyclization reaction. In situ generated aryliodine(III)-fluoride species were used as organocatalysts. Through this oxidative olefin difunctionalization reaction, quaternary C-F stereogenic centers could be constructed with high enantiomeric excesses. DFT calculations enabled deeper understanding of the mechanism and the origin of stereoselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2020. , p. 71
Keywords [en]
fluorination, fluorocyclization, fluorine chemistry, trifluoromethylthiolation, rhodium-catalysis, organocatalysis, asymmetric synthesis, hypervalent iodine, multicomponent reaction, bifunctionalization, diazo compounds
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-180547ISBN: 978-91-7911-138-0 (print)ISBN: 978-91-7911-139-7 (electronic)OAI: oai:DiVA.org:su-180547DiVA, id: diva2:1421054
Public defence
2020-06-01, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Manuscript.

Available from: 2020-05-07 Created: 2020-04-01 Last updated: 2020-05-26Bibliographically approved
List of papers
1. Asymmetric Construction of C-F Quaternary Stereocenters by Organocatalytic Fluorocyclization
Open this publication in new window or tab >>Asymmetric Construction of C-F Quaternary Stereocenters by Organocatalytic Fluorocyclization
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-180193 (URN)
Available from: 2020-04-01 Created: 2020-04-01 Last updated: 2020-04-02Bibliographically approved
2. Trifluoromethylthiolation-Based Bifunctionalization of Diazocarbonyl Compounds by Rhodium Catalysis
Open this publication in new window or tab >>Trifluoromethylthiolation-Based Bifunctionalization of Diazocarbonyl Compounds by Rhodium Catalysis
2017 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 19, no 17, p. 4548-4551Article in journal (Refereed) Published
Abstract [en]

A new Rh-catalyzed, three-component reaction for the oxytrifluoromethylthiolation of alpha-diazoketones was developed. The SCF3 functionality was introduced using a stable dibenzenesulfonimide reagent under mild conditions. Alcohols, acetals, and ethers were used as the alkoxy sources. Cyclic ethers underwent a trifunctionalization reaction through the introduction of SCF3, OR, and N(SO2Ph)(2) substituents in a single step.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-147888 (URN)10.1021/acs.orglett.7b02139 (DOI)000409566400035 ()28816049 (PubMedID)
Available from: 2017-10-23 Created: 2017-10-23 Last updated: 2020-04-19Bibliographically approved
3. Trifluoromethylthiolation-arylation of diazocarbonyl compounds by modified Hooz multicomponent coupling
Open this publication in new window or tab >>Trifluoromethylthiolation-arylation of diazocarbonyl compounds by modified Hooz multicomponent coupling
2019 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 10, no 23, p. 5990-5995Article in journal (Refereed) Published
Abstract [en]

A new Zn-mediated trifluoromethylthiolation-based bifunctionalization reaction is developed. In this process, simultaneous C-SCF3 and C-C bond formation takes place in a multicomponent reaction, in which an aryl and a SCF3 group arise from different reagents. Our studies show that the reaction mechanism is similar to the Hooz multicomponent coupling. The process involves in situ generation of BAr3, which reacts with a diazocarbonyl compound, and the reaction is terminated by an electrophilic SCF3 transfer. The reaction can also be extended to fluorination based bifunctionalization which proceeds with somewhat lower yield than the analogous trifluoromethylthiolation reaction.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-171109 (URN)10.1039/c9sc00829b (DOI)000471133800014 ()
Available from: 2019-08-14 Created: 2019-08-14 Last updated: 2020-04-19Bibliographically approved
4. Synthesis of trifluoromethyl moieties by late-stage copper (I) mediated nucleophilic fluorination
Open this publication in new window or tab >>Synthesis of trifluoromethyl moieties by late-stage copper (I) mediated nucleophilic fluorination
Show others...
2017 (English)In: Journal of fluorine chemistry, ISSN 0022-1139, E-ISSN 1873-3328, Vol. 194, p. 51-57Article in journal (Refereed) Published
Abstract [en]

The nucleophilic fluorination of bromodifluoromethyl derivatives mediated by the complex (PPh3)(3)CuF is described. Under the reaction conditions, different trifluoroacetates, trifluorolcetones, trifluoroarenes and trifluoroacetamides were obtained in good yields.

Keywords
Nucleophilic fluorination, Copper, Trifluoroacetate, Trifluoromethylarene, Trifluoroacetamide
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-141365 (URN)10.1016/j.jfluchem.2016.12.017 (DOI)000393938200007 ()
Available from: 2017-05-02 Created: 2017-05-02 Last updated: 2020-04-01Bibliographically approved

Open Access in DiVA

Bifunctionalization of Small Organic Molecules Based on Fluorine Incorporation(5338 kB)57 downloads
File information
File name FULLTEXT01.pdfFile size 5338 kBChecksum SHA-512
2f34733970e5061bd7e882b6da3908d190ee8c3973e55cadd422505677932e8ad2f3fd846f89863baf8adc88d9b1f3468b95e6d69455062b96f978b7aadde983
Type fulltextMimetype application/pdf

Search in DiVA

By author/editor
Lübcke, Marvin
By organisation
Department of Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 57 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 202 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf