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An umpolung strategy to react catalytic enols with nucleophiles
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0001-9774-0731
Stockholm University, Faculty of Science, Department of Organic Chemistry. Universidad del PaísVasco/UPV-EHU, Spain.
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Number of Authors: 52019 (English)In: Nature Communications, E-ISSN 2041-1723, Vol. 10, article id 5244Article in journal (Refereed) Published
Abstract [en]

The selective synthesis of a-functionalized ketones with two similar enolizable positions can be accomplished using allylic alcohols and iridium(III) catalysts. A formal 1,3-hydrogen shift on allylic alcohols generates catalytic iridium-enolates in a stereospecific manner, which are able to react with electrophiles to yield alpha-functionalized ketones as single constitutional isomers. However, the employment of nucleophiles to react with the nucleophilic catalytic enolates in this chemistry is still unknown. Herein, we report an umpolung strategy for the selective synthesis of alpha-alkoxy carbonyl compounds by the reaction of iridium enolates and alcohols promoted by an iodine(III) reagent. Moreover, the protocol also works in an intra-molecular fashion to synthesize 3(2H)-furanones from gamma-keto allylic alcohols. Experimental and computational investigations have been carried out, and mechanisms are proposed for both the inter- and intramolecular reactions, explaining the key role of the iodine(III) reagent in this umpolung approach.

Place, publisher, year, edition, pages
2019. Vol. 10, article id 5244
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-176494DOI: 10.1038/s41467-019-13175-5ISI: 000497694100012PubMedID: 31748504OAI: oai:DiVA.org:su-176494DiVA, id: diva2:1381761
Available from: 2019-12-27 Created: 2019-12-27 Last updated: 2023-03-28Bibliographically approved
In thesis
1. Multicomponent Catalytic Reactions: Theoretical and Experimental Studies
Open this publication in new window or tab >>Multicomponent Catalytic Reactions: Theoretical and Experimental Studies
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, Density Functional Theory (DFT) methods have been applied to study the mechanisms of three different multicomponent organic reactions. Also, a new synthetic procedure for the preparation of quinolinium salts is presented, and its mechanism also studied by DFT calculations. The thesis summarizes the work realized in two universities, and is divided in the following way: The first part of the thesis concerns the development of an experimentally simple, but mechanistically complex, reaction for the formation of quaternary quinolinium salts catalyzed by palladium salts. This multicomponent process uses readily available propylamine and its derivatives as starting materials. Through DFT studies a mechanism through the activation of two aliphatic C-H bonds is proposed. The second part focuses on the mechanistic investigation of a three-components reaction, namely terminal alkynes, CO2 and allylic chlorides, mediated by an N-heterocyclic carbene catalyst that yields propargylic esters. By DFT calculations, the rate-limiting step was identified to be the reaction between the carboxylated catalyst and the allylic chloride. Through DFT modelling, we were also able to understand the limitations of this reaction. The mechanism of a multicomponent reaction in which allylic alcohols are transformed into α-functionalized carbonyls was also investigated. The reaction relies on an umpolung strategy that enables to react enol intermediates with different nucleophiles. By DFT studies, a mechanism via enolonium intermediates is proposed, which provides an understanding of the selectivity of the reaction. The final chapter of the thesis deals with another multicomponent solvent-free reaction for synthesizing propargylamines catalyzed by manganese via a KA2 coupling. DFT studies were undertaken and a mechanism via manganese phenylacetylide species is proposed.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2021. p. 67
Keywords
C-H Activation, Quaternary Quinolinium, Organocatalyst, Transition Metal Catalyst, Umpolung Strategy, Multi-step Reactions, Mechanistic Investigation, Density Functional Theory
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-195122 (URN)978-91-7911-544-9 (ISBN)978-91-7911-545-6 (ISBN)
Public defence
2021-09-28, online via Zoom, https://stockholmuniversity.zoom.us/j/68655759001, Stockholm, 10:00 (English)
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Available from: 2021-09-03 Created: 2021-08-06 Last updated: 2022-02-25Bibliographically approved

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Sanz-Marco, AmparoMartinez-Erro, SamuelPauze, MartinMartín-Matute, Belén

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