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Transformations of Nitrosoarenes and Alkynyl Enones: Selective Synthesis of Nitrogen-Containing Compounds
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0001-6517-8879
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The nitrogen atom plays a unique role in organic chemistry. It is abundantly found in organic materials and is responsible for the activity of many biologically relevant compounds. In this thesis, nitrosoarenes and keto- and pyridyl-substituted enynes are used as convenient starting materials for the selective synthesis of nitrogen-containing compounds.

Nitrosoarenes are versatile compounds that can undergo a broad range of reactions. The nature of the nitroso group is significantly different from that of related nitrogen-based functional groups and this can be used as an advantage in the development of new methodology. In the first part of this thesis, the para-selective halogenation of nitrosoarenes with copper(II) halides as halogenating reagents is explored. The one-pot transformation of the products to the corresponding nitroarenes and anilines is demonstrated. The use of nitrosoarenes for radical N-perfluoroalkylation is presented in the next chapters. N-Perfluoroalkylation is a relatively new field and only a limited number of reagents and substrates have been employed so far. In this thesis, the stable and convenient Langlois reagent was used to achieve selective N-trifluoromethylation of nitrosoarenes to obtain the corresponding hydroxylamines. Longer perfluoroalkyl chains were investigated as well, but the less stable products were defluorinated to form hydroxamic acid derivatives. These products could be reduced to yield perfluoroalkyl amides.

Keto- and pyridyl-substituted enynes are starting materials designed to undergo cyclization reactions in the presence of a metal catalyst and a nucleophile. This offers the possibility to obtain a variety of more complex molecular structures in a single step. In the second half of the thesis, the reaction between these starting materials and enamines is explored. A range of cyclopenta[c]furans were synthesized in good yields and with high diastereoselectivities from alkynyl enones and enamines with InBr3 as the catalyst. The enamines were formed in situ in a multicomponent reaction. Pyridyl-substituted enynes are the pyridine analogues of alkynyl enones and were found to form polycyclic indolizines in the reaction with cyclic enamines with AgOTf as a catalyst. Good yields and high to excellent diastereoselectivities were obtained. When the reaction was performed with in situ-generated enamines, different indolizine derivatives were obtained.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2018. , p. 72
Keywords [en]
alkynyl enones, catalysis, copper, halogenation, heterocycles, nitrosoarenes, perfluoroalkylation, trifluoromethylation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-155542ISBN: 978-91-7797-091-0 (print)ISBN: 978-91-7797-092-7 (electronic)OAI: oai:DiVA.org:su-155542DiVA, id: diva2:1201413
Public defence
2018-06-15, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript.

Available from: 2018-05-23 Created: 2018-04-25 Last updated: 2018-05-23Bibliographically approved
List of papers
1. Para-Selective Halogenation of Nitrosoarenes with Copper(II) Halides
Open this publication in new window or tab >>Para-Selective Halogenation of Nitrosoarenes with Copper(II) Halides
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 24, p. 6210-6213Article in journal (Refereed) Published
Abstract [en]

The para-selective direct bromination and chlorination of nitrosoarenes with copper(II) bromide and chloride is reported. Under mild reaction conditions, a rang of halogenated arylnitroso compounds are obtained in moderate to good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of a One-pot procedure to obtain the corresponding para-halogenated aniline- and nitrobenzene derivatives.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-126203 (URN)10.1021/acs.orglett.5b03198 (DOI)000366878300069 ()
Funder
Swedish Research Council
Available from: 2016-01-28 Created: 2016-01-26 Last updated: 2018-05-08Bibliographically approved
2. N-Trifluoromethylation of Nitrosoarenes with Sodium Triflinate
Open this publication in new window or tab >>N-Trifluoromethylation of Nitrosoarenes with Sodium Triflinate
2017 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 19, no 9, p. 2374-2377Article in journal (Refereed) Published
Abstract [en]

A highly efficient N-trifluoromethylation of nitro-soarenes is reported. The inexpensive and convenient Langlois reagent (sodium triflinate) is employed as a Ch(3)-radical source in combination with a copper catalyst and an oxidant. N-Trifluoromethylated hychoxylamines are obtained in high yields within 1 h at room temperature. The addition of hydroquinone was found to be instrumental to prevent the formation of side products. The method is high-yielding is scalable, and displays a high functional group tolerance.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-144846 (URN)10.1021/acs.orglett.7b00908 (DOI)000401044500045 ()28402669 (PubMedID)
Funder
Swedish Research Council
Available from: 2017-07-04 Created: 2017-07-04 Last updated: 2018-05-08Bibliographically approved
3. N-Perfluoroalkylation of Nitrosoarenes with Perfluoroalkanesulfinates
Open this publication in new window or tab >>N-Perfluoroalkylation of Nitrosoarenes with Perfluoroalkanesulfinates
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-155541 (URN)
Available from: 2018-04-24 Created: 2018-04-24 Last updated: 2018-05-08Bibliographically approved
4. Diastereoselective Synthesis of Cyclopenta[c]furans by a Catalytic Multicomponent Reaction
Open this publication in new window or tab >>Diastereoselective Synthesis of Cyclopenta[c]furans by a Catalytic Multicomponent Reaction
2016 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 55, no 39, p. 11863-11866Article in journal (Refereed) Published
Abstract [en]

A diastereoselective three-component reaction between alkynyl enones, aldehydes and secondary amines is reported. With the aid of a benign indium catalyst, a range of highly substituted cyclopenta[c]furan derivatives can be obtained in a single-step procedure. The formation of the stereodefined heterocyclic motifs takes place via in situ generation of enamines followed by two sequential cyclization steps.

Keywords
alkynes, enones, fused-ring systems, indium catalysis, multicomponent reactions
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-134923 (URN)10.1002/anie.201606108 (DOI)000384713100026 ()27538999 (PubMedID)
Funder
Swedish Research Council
Available from: 2016-10-25 Created: 2016-10-25 Last updated: 2018-04-25Bibliographically approved
5. Diastereoselective Synthesis of Polycyclic Indolizines with 2‑(2‑Enynyl)pyridines and Enamines
Open this publication in new window or tab >>Diastereoselective Synthesis of Polycyclic Indolizines with 2‑(2‑Enynyl)pyridines and Enamines
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-153087 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2018-05-08Bibliographically approved

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