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Diastereoselective Synthesis of Cyclopenta[c]furans by a Catalytic Multicomponent Reaction
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-6536-8506
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0001-6517-8879
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-9085-0476
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.

Place, publisher, year, edition, pages
2016. Vol. 55, no 39, p. 11863-11866
Keywords [en]
alkynes, enones, fused-ring systems, indium catalysis, multicomponent reactions
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-134923DOI: 10.1002/anie.201606108ISI: 000384713100026PubMedID: 27538999OAI: oai:DiVA.org:su-134923DiVA, id: diva2:1039877
Funder
Swedish Research CouncilAvailable from: 2016-10-25 Created: 2016-10-25 Last updated: 2018-04-25Bibliographically approved
In thesis
1. Development of new Catalytic Methods for the Selective Synthesis of Heterocycles
Open this publication in new window or tab >>Development of new Catalytic Methods for the Selective Synthesis of Heterocycles
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the field of organic chemistry, the development of new catalytic methods for the synthesis of complex molecules from simple precursors is a top priority. The main focus of this thesis concerns the diastereoselective synthesis of heterocyclic compounds using main group elements as Lewis acid catalysts.

The first part of this thesis deals with an annulation reaction of nitrones with oxiranes, aziridines, and thiiranes using Al(III) or In(III) catalysts. From this protocol, 1,4,2-dioxazinanes, 1,2,4-oxadiazinanes, and 1,4,2-oxathiazinanes were obtained in moderate to high yields with excellent diastereoselectivity. The transformation was found to be stereospecific and proceed via an SN2-mechanism.

The second and third parts concern the development of In(III)-catalyzed annulation of carbonyl compounds, amines, and alkynyl enones. InBr3 was found to be an efficient catalyst for the activation of alkynyl enones in a multicomponent reaction with aldehydes and amines. The method affords cyclopenta[c]furans in high yields and in good to excellent diastereomeric ratios. Bicyclo[3.n.1]alkenone derivatives were formed via a double Michael addition reaction of cyclic ketones, amines, and alkynyl enones, in the presence of InCl3. The utility of these protocols was also demonstrated by sequential transformations.

In the fourth part, AgOTf and CuI were found to be efficient catalysts for the activation of pyridine-substituted enynes towards enamines, providing indolizine derivatives in high yield and good diastereomeric ratios.

In the last part of the thesis, 1,2-aminoarylation of γ,δ-unsaturated oxime esters with arylboronic acids using Ni catalysis is discussed. The protocol demonstrates the potential of Ni-catalysts for the generation of iminyl radicals to furnish functionalized pyrroline derivatives. The utility of this protocol was exemplified by transforming the pyrroline products to the corresponding pyrrole and pyrrolidine derivatives. 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2018. p. 65
Keywords
catalysis, indium, heterocycles, Lewis acid, multicomponent reactions, furans, alkynes
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-153088 (URN)978-91-7797-093-4 (ISBN)978-91-7797-094-1 (ISBN)
Public defence
2018-04-06, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.

Available from: 2018-03-14 Created: 2018-02-20 Last updated: 2018-06-08Bibliographically approved
2. Transformations of Nitrosoarenes and Alkynyl Enones: Selective Synthesis of Nitrogen-Containing Compounds
Open this publication in new window or tab >>Transformations of Nitrosoarenes and Alkynyl Enones: Selective Synthesis of Nitrogen-Containing Compounds
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
alkynyl enones, catalysis, copper, halogenation, heterocycles, nitrosoarenes, perfluoroalkylation, trifluoromethylation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-155542 (URN)978-91-7797-091-0 (ISBN)978-91-7797-092-7 (ISBN)
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

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Pathipati, Stalin R.van der Werf, AngelaEriksson, LarsSelander, Nicklas
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