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Novel strategies for C-C/X bond formation
Linnaeus University, Faculty of Health and Life Sciences, Department of Chemistry and Biomedical Sciences.ORCID iD: 0000-0003-1981-4533
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The formation of C-C/X bonds is essential for the manufacture of a broad range of chemicals and materials used in areas critical for maintaining quality of life in modern society, e.g. pharmaceuticals, agrochemicals and polymers, and for aspects of research in organic chemistry. The use of catalysts for facilitating these reactions is highly desirable due to the improvements in energy and atom economies that can potentially be achieved.The primary objective of the thesis was to explore novel approaches for catalysis of C-C/X bond-forming reactions, both through C-H activation. In paper I, at unable cobalt catalyzed C-H activation-driven annulation of benzamides with unsymmetrical diynes was developed, where either 3- or 4-substitution of the isoquinolone could be steered by the nature of the diyne used. Anunprecedented iridium catalyzed tandem bis-arylsulfenylation of indoles was described (paper II), where an adamantoyl sacrificial directing group plays a key role in the simultaneous direction of arylsulfenylation to the 2- and 4- positions. In paper III, a flow reactor in a lab-on-a-chip device was developed for the Suzuki cross-coupling reaction. Miniaturization provides the opportunity to reduce material consumption. Polyethyleneimine (PEI)-brushes were used for the immobilization of Pd-nanoparticles, and high efficiencies were observed. Collectively, the research underpinning this thesis provides new strategies forC-C and C-X(S) bond formation.

Place, publisher, year, edition, pages
Linnaeus University Press, 2022. , p. 70
Series
Linnaeus University Dissertations ; 470
Keywords [en]
annulation, C-H activation, heterocycles, heterogeneous catalysis, homogeneous catalysis, lab-on-a-chip, Suzuki cross-coupling
National Category
Organic Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
URN: urn:nbn:se:lnu:diva-118648DOI: 10.15626/LUD.470.2022ISBN: 9789189709621 (print)ISBN: 9789189709638 (electronic)OAI: oai:DiVA.org:lnu-118648DiVA, id: diva2:1729923
Public defence
2022-11-18, Azur, Hus Vita, Kalmar, 09:30 (English)
Opponent
Supervisors
Available from: 2023-01-23 Created: 2023-01-23 Last updated: 2025-03-05Bibliographically approved
List of papers
1. Tandem Iridium-Catalyzed Decarbonylative C-H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation
Open this publication in new window or tab >>Tandem Iridium-Catalyzed Decarbonylative C-H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation
2021 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 23, no 9, p. 3331-3336Article in journal (Refereed) Published
Abstract [en]

Described herein is a decarbonylative tandem C-H bis-arylsulfenylation of indole at the C2 and C4 C-H bonds through the use of pentamethylcyclopentadienyl iridium dichloride dimer ([Cp*IrCl2](2)) catalyst and disulfides. A new sacrificial electron-rich adamantoyl-directing group facilitates indole C-H bis-functionalization with a traceless in situ removal. Various differently substituted disulfides can be easily accommodated in this reaction by a coordination to Ir(III) through the formation of six- and five-membered iridacycles at the C2 and C4 positions, respectively. Mechanistic studies show that a C-H activation-induced C-C activation is involved in the catalytic cycle.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2021
National Category
Organic Chemistry
Research subject
Chemistry, Organic Chemistry
Identifiers
urn:nbn:se:lnu:diva-104505 (URN)10.1021/acs.orglett.1c00829 (DOI)000649477300020 ()33908788 (PubMedID)2-s2.0-85106511554 (Scopus ID)2021 (Local ID)2021 (Archive number)2021 (OAI)
Available from: 2021-06-11 Created: 2021-06-11 Last updated: 2025-09-23Bibliographically approved
2. Palladium nanoparticles immobilized on polyethylenimine-derivatized gold surfaces for catalysis of Suzuki reactions: development and application in a lab-on-a-chip context
Open this publication in new window or tab >>Palladium nanoparticles immobilized on polyethylenimine-derivatized gold surfaces for catalysis of Suzuki reactions: development and application in a lab-on-a-chip context
2021 (English)In: RSC Advances, E-ISSN 2046-2069, Vol. 11, no 56, p. 35161-35164Article in journal (Refereed) Published
Abstract [en]

Gold surface-bound hyperbranched polyethyleneimine (PEI) films decorated with palladium nanoparticles have been used as efficient catalysts for a series of Suzuki reactions. This thin film-format demonstrated good catalytic efficiency (TON up to 3.4 x 10(3)) and stability. Incorporation into a quartz crystal microbalance (QCM) instrument illustrated the potential for using this approach in lab-on-a-chip-based synthesis applications.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2021
National Category
Chemical Sciences
Research subject
Natural Science, Chemistry
Identifiers
urn:nbn:se:lnu:diva-108228 (URN)10.1039/d1ra06851b (DOI)000712916300001 ()2-s2.0-85119853402 (Scopus ID)2021 (Local ID)2021 (Archive number)2021 (OAI)
Note

Correction published in: RSC Adv., 2022,12, 34568-34569, https://doi.org/10.1039/D2RA90120J

Available from: 2021-11-26 Created: 2021-11-26 Last updated: 2025-09-23Bibliographically approved

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Anaspure, Prasad

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