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Palladium(II)-Catalyzed Oxidative Carbocyclization/Functionalization of Allenynes
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2014 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

The selective formation of carbon-carbon bonds constitutes a key transformation in organic synthesis with useful applications in pharmaceutical or material industry. A particularly versatile tool for carbon-carbon as well as carbon-heteroatom bond formation is palladium catalysis, which allows for mild and selective routes even towards complex structures.

The work in this thesis describes the development and the mechanistic investigation of a palladium(II)-catalyzed oxidative carbocyclization/functionalization methodology, which converts 1,5-allenynes into either arylated or borylated carbocycles. To this end, either boronic acids or B2pin2 are employed and 1,4-benzoquinone serves as the stoichiometric oxidant. These protocols provide access to two products, a cyclic triene and a cyclic vinylallene. Their formation is dependent on the substrate structure as the latter product requires a propargylic C–H bond to be present in the substrate. Based on kinetic isotope effects, mechanisms involving either an initial allenic or propargylic C–H abstraction, respectively, were proposed. Full control of product selectivity to give either trienes or vinylallenes was achieved by modifying the reaction conditions with additives. Using substoichiometric amounts of BF3·OEt2 leads selectively to borylated or arylated vinylallenes. Under arylating conditions the reaction is zero order in allenyne and oxidant, and first order in phenylboronic acid. Transmetalation and, to some extent, propargylic C–H cleavage were found to be turnover-limiting. The selective reaction towards functionalized trienes was achieved by addition of either substoichiometric LiOAc·2H2O (borylation) or excess amounts of H2O (arylation). For the latter case, a kinetic study revealed an unusually slow catalyst activation. Lower concentrations of H2O gave product mixtures, and it was shown that vinylallenes are formed with either boronic acid or boroxine, whereas the formation of trienes requires boronic acid.

sted, utgiver, år, opplag, sider
Stockholm: Department of Organic Chemistry, Stockholm University , 2014. , s. 95
Emneord [en]
palladium catalysis, oxidation, carbocyclization, allenynes, boron reagents, kinetics, selectivity, reaction mechanism
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-108587ISBN: 978-91-7649-019-8 (tryckt)OAI: oai:DiVA.org:su-108587DiVA, id: diva2:759706
Disputas
2014-12-04, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (engelsk)
Opponent
Veileder
Merknad

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Tilgjengelig fra: 2014-11-12 Laget: 2014-10-30 Sist oppdatert: 2014-11-21bibliografisk kontrollert
Delarbeid
1. Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
Åpne denne publikasjonen i ny fane eller vindu >>Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
Vise andre…
2012 (engelsk)Inngår i: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 51, nr 11, s. 2703-2707Artikkel i tidsskrift (Fagfellevurdert) Published
Emneord
alkynes, allenes, cyclization, oxidation, palladium
HSV kategori
Identifikatorer
urn:nbn:se:su:diva-78438 (URN)10.1002/anie.201107592 (DOI)000301173800031 ()
Forskningsfinansiär
Swedish Research Council
Merknad

5

Tilgjengelig fra: 2012-07-05 Laget: 2012-07-04 Sist oppdatert: 2017-12-07bibliografisk kontrollert
2. Control of Selectivity in Palladium-Catalyzed Oxidative Carbocyclization/Borylation of Allenynes
Åpne denne publikasjonen i ny fane eller vindu >>Control of Selectivity in Palladium-Catalyzed Oxidative Carbocyclization/Borylation of Allenynes
2013 (engelsk)Inngår i: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, nr 24, s. 6283-6287Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

In control: A highly selective carbocyclization/borylation of allenynes with bis(pinacolato)diboron (B2pin2) under palladium catalysis and with p-benzoquinone (BQ) as the oxidant was developed. The use of either LiOAc⋅2 H2O with 1,2-dichloroethane (DCE) as the solvent or BF3⋅Et2O together with THF is crucial for the selective formation of borylated trienes and vinylallenes, respectively.

Emneord
allenes, boronates, cyclization, oxidation, palladium
HSV kategori
Identifikatorer
urn:nbn:se:su:diva-90111 (URN)10.1002/anie.201301167 (DOI)000320375800028 ()
Forskningsfinansiär
EU, European Research Council, 247014Swedish Research CouncilKnut and Alice Wallenberg FoundationThe Wenner-Gren FoundationBerzelii Centre EXSELENT
Merknad

AuthorCount: 3;

Tilgjengelig fra: 2013-05-23 Laget: 2013-05-23 Sist oppdatert: 2017-12-06bibliografisk kontrollert
3. Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes: Control of Selectivity and Role of H2O
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Vise andre…
2014 (engelsk)Inngår i: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, nr 33, s. 8696-8699Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Highly selective protocols for the carbocyclization/arylation of allenynes using arylboronic acids are reported. Arylated vinylallenes are obtained with the use of BF3 center dot Et2O as an additive, whereas addition of water leads to arylated trienes. These conditions provide the respective products with excellent selectivities (generally > 97:3) for a range of boronic acids and different allenynes. It has been revealed that water plays a crucial role for the product distribution.

sted, utgiver, år, opplag, sider
Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2014
Emneord
allenes, boronic acids, cyclization, oxidation, palladium
HSV kategori
Identifikatorer
urn:nbn:se:su:diva-107580 (URN)10.1002/anie.201404264 (DOI)000340523500025 ()
Forskningsfinansiär
Knut and Alice Wallenberg FoundationEU, European Research CouncilSwedish Research CouncilBerzelii Centre EXSELENTThe Wenner-Gren Foundation
Merknad

AuthorCount:5;

Tilgjengelig fra: 2014-09-21 Laget: 2014-09-20 Sist oppdatert: 2017-12-05bibliografisk kontrollert
4. Complex Kinetics in a Palladium(II)-Catalyzed Oxidative Carbocyclization: Untangling of Competing Pathways, Pre-Catalyst Activation, and Product Mixtures
Åpne denne publikasjonen i ny fane eller vindu >>Complex Kinetics in a Palladium(II)-Catalyzed Oxidative Carbocyclization: Untangling of Competing Pathways, Pre-Catalyst Activation, and Product Mixtures
Vise andre…
(engelsk)Manuskript (preprint) (Annet vitenskapelig)
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-108586 (URN)
Tilgjengelig fra: 2014-10-30 Laget: 2014-10-30 Sist oppdatert: 2014-11-03

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