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Development of new Catalytic Methods for the Selective Synthesis of Heterocycles
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Dr. Nicklas Selander)ORCID iD: 0000-0002-6536-8506
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 [en]
catalysis, indium, heterocycles, Lewis acid, multicomponent reactions, furans, alkynes
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-153088ISBN: 978-91-7797-093-4 (print)ISBN: 978-91-7797-094-1 (electronic)OAI: oai:DiVA.org:su-153088DiVA, id: diva2:1184039
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
List of papers
1. Lewis Acid Catalyzed Annulation of Nitrones with Oxiranes, Aziridines, and Thiiranes
Open this publication in new window or tab >>Lewis Acid Catalyzed Annulation of Nitrones with Oxiranes, Aziridines, and Thiiranes
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 18, p. 4506-4509Article in journal (Refereed) Published
Abstract [en]

A highly selective Lewis acid catalyzed annulation of three-membered heterocycles with nitrones has been developed. Oxiranes, aziridines, and thiiranes were used as substrates for the synthesis of various six-membered heterocycles using Al or In catalysts. This catalytic protocol demonstrates a broad substrate scope and provides access to new structural motifs in high yields and in excellent selectivity under mild reaction conditions.

National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-122328 (URN)10.1021/acs.orglett.5b02195 (DOI)000361867800028 ()
Funder
Swedish Research CouncilLars Hierta Memorial FoundationKnut and Alice Wallenberg Foundation
Available from: 2015-12-01 Created: 2015-10-29 Last updated: 2018-02-20Bibliographically approved
2. 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
3. Stereoselective synthesis of bicyclo[3.n.1]alkenone frameworks by Lewis acid-catalysis
Open this publication in new window or tab >>Stereoselective synthesis of bicyclo[3.n.1]alkenone frameworks by Lewis acid-catalysis
2017 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 53, no 82, p. 11353-11356Article in journal (Refereed) Published
Abstract [en]

An intermolecular cyclization of alkynyl enones with cyclic ketones for the synthesis of bicyclo[3.n.1]alkenones is reported. This protocol exhibits a high functional group tolerance and provides access to a variety of bicyclic systems found as skeletons in many natural products.

National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-148991 (URN)10.1039/c7cc06400d (DOI)000412814900017 ()28967928 (PubMedID)
Available from: 2017-11-28 Created: 2017-11-28 Last updated: 2018-02-20Bibliographically approved
4. 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
5. Nickel-Catalyzed 1,2-Aminoarylation of Oxime Ester-Tethered Alkenes with Boronic Acids
Open this publication in new window or tab >>Nickel-Catalyzed 1,2-Aminoarylation of Oxime Ester-Tethered Alkenes with Boronic Acids
2017 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 7, no 12, p. 8441-8445Article in journal (Refereed) Published
Abstract [en]

A nickel-catalyzed 1,2-aminoarylation of oximeester-tethered alkenes with boronic acids was developed. A variety of pyrroline derivatives were synthesized in good yields via the successive formation of C(sp(3))-N and C(sp(3))-C(sp(2)) bonds. For cyclobutanone-derived oxime esters, the reaction provided aliphatic nitriles incorporating an aromatic group in the gamma-position. A mechanism involving iminyl radical and carbon-centered radical intermediates was proposed.

Keywords
aminoarylation, nickel catalysis, oximes, pyrrolines, radicals
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-151159 (URN)10.1021/acscatal.7b03432 (DOI)000417230500050 ()
Available from: 2018-01-16 Created: 2018-01-16 Last updated: 2018-02-20Bibliographically approved

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