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Novel Metal-Mediated Organic Transformations: Focusing on Microwave Acceleration and the Oxidative Heck Reaction
Uppsala University, Medicinska vetenskapsområdet, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Transition metals have played an important role in synthetic organic chemistry for more than a century, and offer catalytic transformations that would have been impossible with classical chemistry. One of the most useful and versatile of the transition metals is palladium, which over the years has catalyzed many important carbon-carbon forming reactions. Popular cross-coupling reactions such as the Suzuki, Stille and the Heck reaction are all catalyzed by palladium, or more correctly, by palladium in its ground state, Pd(0).

Recently, interest in palladium(II)-catalyzed transformations has started to grow, partly due to the development of the vinylic substitution reaction, commonly called the oxidative Heck reaction, presented in this thesis. This Pd(II)-catalyzed, ligand-modulated reaction occurs under air at room temperature, and for the first time a general protocol employing a wide range of olefins and arylboronic acids was obtained. Ligand screening showed that the bidentate nitrogen ligand, 2,9-dimethyl-1,10-phenanthroline (dmphen), was the most suitable ligand. Dmphen is believed to facilitate regeneration of active Pd(II), increase catalytic stability and improve the regioselectivity in the reaction. A mechanistic investigation was conducted using electrospray ionization mass spectrometry (ESI-MS), making it possible to observe cationic intermediates in a productive oxidative Heck arylation. The results obtained are in agreement with the previously proposed catalytic cycle.

The emerging discipline of high-speed synthesis is making contributions to society’s growing demand for new chemical entities. This inspired the development of two ultrafast, microwave-accelerated carbonylation reactions with dicobalt octacarbonyl acting both as an in situ carbon monoxide supplier and reaction mediator. A wide range of symmetrical benzophenones was produced in only 6 to 10 s, using aryl iodides as the substrate. The second carbonylation reaction provided symmetrical and unsymmetrical ureas in process times ranging from 10 s to 40 minutes using primary and secondary amines.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2006. , p. 77
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Pharmacy, ISSN 1651-6192 ; 37
Keywords [en]
Organic chemistry, palladium(II), oxidative Heck reaction, high-throughput-chemistry, microwave acceleration, dicobalt octacarbonyl, in situ carbonylation, urea, diaryl ketones, ESI-MS
Keywords [sv]
Organisk kemi
Identifiers
URN: urn:nbn:se:uu:diva-7117ISBN: 91-554-6638-9 (print)OAI: oai:DiVA.org:uu-7117DiVA, id: diva2:168779
Public defence
2006-10-06, B41, BMC, Husargatan 3, Uppsala, 09:15
Opponent
Supervisors
Available from: 2006-09-14 Created: 2006-09-14Bibliographically approved
List of papers
1. Open-air oxidative Heck reactions at room temperature
Open this publication in new window or tab >>Open-air oxidative Heck reactions at room temperature
2006 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 8, no 4, p. 338-343Article in journal (Refereed) Published
Abstract [en]

Palladium(II)-catalyzed oxidative Heck arylation reactions proceed at room temperature with atmospheric air as the sole reoxidant. Using arylboronic acids as arylating agents and inexpensive 2,9-dimethyl-1,10-phenanthroline as the supporting ligand, efficient vinylic substitution reactions were obtained both with electron-poor and electron-rich olefins on a 1–50 mmol scale.

National Category
Medical and Health Sciences
Identifiers
urn:nbn:se:uu:diva-94792 (URN)10.1039/B517152K (DOI)
Available from: 2006-09-14 Created: 2006-09-14 Last updated: 2017-12-14Bibliographically approved
2. ESI-MS Detection of Proposed Reaction Intermediates in the Air-Promoted and Ligand-Modulated Oxidative Heck Reaction
Open this publication in new window or tab >>ESI-MS Detection of Proposed Reaction Intermediates in the Air-Promoted and Ligand-Modulated Oxidative Heck Reaction
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 23, p. 8779-8786Article in journal (Refereed) Published
Abstract [en]

Electrospray ionization mass spectrometry (ESI-MS) and subsequent MS/MS analyses were used to directly detect palladium-containing cationic reaction intermediates in a ligand controlled palladium(II)-catalyzed oxidative Heck arylation. All potential intermediates were observed as dmphen-ligated palladium(II) species, suggesting that the dmphen bidentate ligand is attached to the metal center during the entire catalytic cycle. The study supports previous mechanistic propositions and provides new information regarding the composition of aryl-containing Pd(II) complexes in an ongoing oxidative Heck reaction. In addition, sodium acetate was found to be a useful base alternative to previously used tertiary amines.

National Category
Pharmaceutical Sciences
Identifiers
urn:nbn:se:uu:diva-94793 (URN)10.1021/jo061437d (DOI)000241755300013 ()17081006 (PubMedID)
Available from: 2006-09-14 Created: 2006-09-14 Last updated: 2018-06-04Bibliographically approved
3. Ultrafast Chemistry: Cobalt Carbonyl-Mediated Synthesis of Diaryl Ketones under Microwave Irradiation
Open this publication in new window or tab >>Ultrafast Chemistry: Cobalt Carbonyl-Mediated Synthesis of Diaryl Ketones under Microwave Irradiation
2003 (English)In: Organic Letters, ISSN 1523-7060, Vol. 5, no 25, p. 4875-4878Article in journal (Refereed) Published
National Category
Medical and Health Sciences
Identifiers
urn:nbn:se:uu:diva-94794 (URN)
Available from: 2006-09-14 Created: 2006-09-14 Last updated: 2013-07-04Bibliographically approved
4. Super fast cobalt carbonyl-mediated synthesis of ureas
Open this publication in new window or tab >>Super fast cobalt carbonyl-mediated synthesis of ureas
2005 (English)In: Tetrahedron Letters, ISSN 0040-4039, Vol. 46, no 19, p. 3335-3339Article in journal (Refereed) Published
National Category
Medical and Health Sciences
Identifiers
urn:nbn:se:uu:diva-94795 (URN)
Available from: 2006-09-14 Created: 2006-09-14 Last updated: 2013-07-04Bibliographically approved

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