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Copper-catalyzed synthesis of allenylboronic acids. Access to sterically encumbered homopropargylic alcohols and amines by propargylboration
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-5402-8418
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-8834-9834
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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Number of Authors: 72018 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 9, no 13, p. 3305-3312Article in journal (Refereed) Published
Abstract [en]

Tri- and tetrasubstituted allenylboronic acids were prepared via a new versatile copper-catalyzed methodology. The densely functionalized allenylboronic acids readily undergo propargylboration reactions with ketones and imines without any additives. Catalytic asymmetric propargylborylation of ketones is demonstrated with high stereoselectivity allowing for the synthesis of highly enantioenriched tertiary homopropargyl alcohols. The reaction is suitable for kinetic resolution of racemic allenylboronic acids affording alkynes with adjacent quaternary stereocenters.

Place, publisher, year, edition, pages
2018. Vol. 9, no 13, p. 3305-3312
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-156740DOI: 10.1039/c7sc05123aISI: 000431113300006PubMedID: 29732108OAI: oai:DiVA.org:su-156740DiVA, id: diva2:1219862
Available from: 2018-06-18 Created: 2018-06-18 Last updated: 2022-03-23Bibliographically approved
In thesis
1. Synthesis of Organoboronic Acids and Applications in Asymmetric Organocatalysis
Open this publication in new window or tab >>Synthesis of Organoboronic Acids and Applications in Asymmetric Organocatalysis
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Allyl- and allenylboronic acids are valuable reagents in organic synthesis due to their configurational stability and high reactivity. Few allyl- and allenylboronates are commercially available. Therefore, both the preparation and synthetic application of these organoboronic acids are subjects of study. A copper-catalyzed method for the synthesis of tetrasubstituted allenylboronic acids is presented in this thesis. Several enantioselective applications of these allenylboronic acids are presented, including the synthesis of chiral α-amino acid derivatives. Applications of γ,γ-disubstituted allylboronic acids in asymmetric organocatalysis are also presented in this thesis. Varying the E-Z geometry of the allylboron reagents allowed for stereodivergent synthesis of products bearing up to three stereocenters. A common element in the asymmetric methodologies described in this thesis is the application of BINOL-type organocatalysts. The most notable example is the methodology developed for the preparation of α-chiral allylboronic acids via asymmetric homologation of olefinic boronic acids. The resulting chiral boronic acids are of high synthetic interest, which is demonstrated by the wide variety of synthetic applications including allylboration, oxidation, and a purification sequence leading to isolated α-chiral allylboronic acids.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2021. p. 75
Keywords
Boronic acid, BINOL, allylboration, propargylation, homologation, stereoselective synthesis, asymmetric synthesis, organocatalysis, allylboronic acid, allenylboronic acid
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-187390 (URN)978-91-7911-388-9 (ISBN)978-91-7911-389-6 (ISBN)
Public defence
2021-02-12, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (English)
Opponent
Supervisors
Available from: 2021-01-20 Created: 2020-12-09 Last updated: 2022-02-25Bibliographically approved
2. Synthesis of Organofluorine Compounds and Allenylboronic Acids - Applications Including Fluorine-18 Labelling
Open this publication in new window or tab >>Synthesis of Organofluorine Compounds and Allenylboronic Acids - Applications Including Fluorine-18 Labelling
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This work is focused on two areas: the chemistry of organofluorine and organoboron compounds. In the first chapter, a copper-catalysed synthesis of tri- and tetrasubstituted allenylboronic acids is presented. Extension of the same method leads to allenylboronic esters. The very reactive and moisture-sensitive allenylboronic acids are further applied to the reaction with aldehydes, ketones and imines to form homopropargyl alcohols and amines. In addition, an enantioselective reaction catalysed by a BINOL organocatalyst was developed to form tertiary alcohols with adjacent quaternary carbon stereocenters.

The second chapter specialises in the functionalisation of 2,2-difluoro enol silyl ethers with electrophilic reagents under mild reaction conditions. This allowed for the formation of perfluoroethyl ketones, 2-aryl-2,2-difluoro ketones as well as the novel -COCF2SCF3-moiety. 

The third chapter continues with electrophilic fluorination. A synthesis of an electrophilic, 18F-labelled hypervalent iodine reagent from nucleophilic 18F-labelled tetrabutylammonium fluoride was devised. Then, the 18F-labelling of o-styryl benzamides using the developed reagent afforded [18F]benzoxazepines in good radiochemical yields and molar activity.

The objective of the final chapter was the development of a method for the nucleophilic 18F-labelling of 2-halo-2,2-difluoro ketones derived from the corresponding 2,2-difluoro enol silyl ethers. The radiochemical utility of this method was demonstrated by fluorine-18 labelling of a potential neutrophil elastase ligand followed by successful preclinical studies.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2021. p. 73
Keywords
boron, allenylboronic acid, BINOL, homopropargyl alcohol, organocatalyst, organoboron, organofluorine, fluorine, fluorine-18, late-stage, labelling, labeling, nucleophilic, electrophilic, fluorination, positron emision tomography, PET, radiotracer, hypervalent iodine, benziodoxole, benzoxazepines, diaryliodonium salt, metal-free, neutrophil elastase, NE, neutrophil elastase inhibitor, trifluoromethylation, trifluoromethylthiolation, difluoro enol silyl ethers
National Category
Organic Chemistry Natural Sciences Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-192156 (URN)978-91-7911-490-9 (ISBN)978-91-7911-491-6 (ISBN)
Public defence
2021-06-04, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2021-05-11 Created: 2021-04-15 Last updated: 2022-02-25Bibliographically approved

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Jonker, Sybrand J. T.Meyer, Denise N.Eriksson, LarsSzabó, Kálmán J.

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