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ESI-MS Detection of Proposed Reaction Intermediates in the Air-Promoted and Ligand-Modulated Oxidative Heck Reaction
Uppsala universitet, Medicinska och farmaceutiska vetenskapsområdet, Farmaceutiska fakulteten, Institutionen för läkemedelskemi, Avdelningen för organisk farmaceutisk kemi.
Uppsala universitet, Medicinska och farmaceutiska vetenskapsområdet, Farmaceutiska fakulteten, Institutionen för läkemedelskemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för fysikalisk och analytisk kemi.
Uppsala universitet, Medicinska och farmaceutiska vetenskapsområdet, Farmaceutiska fakulteten, Institutionen för läkemedelskemi.
2006 (Engelska)Ingår i: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, nr 23, s. 8779-8786Artikel i tidskrift (Refereegranskat) 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.

Ort, förlag, år, upplaga, sidor
2006. Vol. 71, nr 23, s. 8779-8786
Nationell ämneskategori
Farmaceutiska vetenskaper
Identifikatorer
URN: urn:nbn:se:uu:diva-94793DOI: 10.1021/jo061437dISI: 000241755300013PubMedID: 17081006OAI: oai:DiVA.org:uu-94793DiVA, id: diva2:168776
Tillgänglig från: 2006-09-14 Skapad: 2006-09-14 Senast uppdaterad: 2018-06-04Bibliografiskt granskad
Ingår i avhandling
1. Novel Metal-Mediated Organic Transformations: Focusing on Microwave Acceleration and the Oxidative Heck Reaction
Öppna denna publikation i ny flik eller fönster >>Novel Metal-Mediated Organic Transformations: Focusing on Microwave Acceleration and the Oxidative Heck Reaction
2006 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Uppsala: Acta Universitatis Upsaliensis, 2006. s. 77
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Pharmacy, ISSN 1651-6192 ; 37
Nyckelord
Organic chemistry, palladium(II), oxidative Heck reaction, high-throughput-chemistry, microwave acceleration, dicobalt octacarbonyl, in situ carbonylation, urea, diaryl ketones, ESI-MS, Organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-7117 (URN)91-554-6638-9 (ISBN)
Disputation
2006-10-06, B41, BMC, Husargatan 3, Uppsala, 09:15
Opponent
Handledare
Tillgänglig från: 2006-09-14 Skapad: 2006-09-14Bibliografiskt granskad

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