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Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-8257-8708
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-5212-8255
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-7826-6445
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Number of Authors: 62023 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 29, no 3, article id e202203130Article in journal (Refereed) Published
Abstract [en]

A novel iron-catalyzed borylation of propargylic acetates leading to allenylboronates has been developed. The method allows the preparation of a variety of di-, tri- and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-SN2’ displacement of acetate by boron occurs; this also allows transfer of chirality to yield enantiomerically enriched allenylboronates. The synthetic utility of this protocol was further substantiated by transformations of the obtained allenylboronates including oxidation and propargylation. 

Place, publisher, year, edition, pages
2023. Vol. 29, no 3, article id e202203130
Keywords [en]
Allenes, allenylboronates, borylation, iron, propargyl esters
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-213118DOI: 10.1002/chem.202203130ISI: 000888153700001PubMedID: 36250587Scopus ID: 2-s2.0-85143203381OAI: oai:DiVA.org:su-213118DiVA, id: diva2:1721016
Available from: 2022-12-20 Created: 2022-12-20 Last updated: 2025-01-14Bibliographically approved
In thesis
1. Advances in Sustainable Catalytic Transformations for Organic Synthesis
Open this publication in new window or tab >>Advances in Sustainable Catalytic Transformations for Organic Synthesis
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The use of metal catalysts is key for many chemical industrial processes. Many of these rely on noble metals which, despite their excellent performance, are scarce and present environmental and societal challenges. Thus, the development of alternative and sustainable synthetic protocols are of utmost importance. Transitioning to abundant metals, such as first-row transition metals (also known as base metals), is the most logical and preferred strategy. However, this transition is not straightforward due to the different reactivity that these metals present. Another strategy to minimize the impact of noble metals is to use them in a more efficient manner.

The work of this thesis contributes to the development of synthetic methods for organic chemistry motivated by sustainability aspects. The strategies explored were transitioning to base metal catalysis, use of light and electricity as energy sources, and the immobilization of homogeneous catalysts. First, a method was developed using an iron complex for the synthesis of allenylboronates from propargyl acetates. Secondly, a heterogeneous photocatalyst PCN-222(Pd) was developed and used for the aerobic cross-condensation of amines. Thirdly, the immobilization of Ru(BINAP)(OAc)2 on cellulose was developed and used for the asymmetric hydrogenation of aliphatic α,β-unsaturated carboxylic acids. Finally, the use of nickel foam as electrocatalyst for the hydrogenation of alkenes was investigated and compared with the traditional Pd/C and H2 gas method via life cyle, toxicological and safety assessments. 

Although catalysis is a tool that can assist in achieving this goal, it is important to highlight that many other aspects require attention, such as recyclability, the use of greener solvents, transition to renewable feedstocks like bio-ethanol, and shorter synthetic protocols, to name a few.

Finally, it is important to understand that addressing all the sustainability aspects of an organic chemistry process is very challenging. However, the improvement of part of these aspects can contribute to the development of a sustainable chemistry in a step-wise manner. 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2025. p. 78
Keywords
Catalysis, Sustainability, Photochemistry, Electrochemistry, Organic Synthesis, Cellulose
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-237931 (URN)978-91-8107-078-1 (ISBN)978-91-8107-079-8 (ISBN)
Public defence
2025-02-24, Magneli Salen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16B, Stockholm, 09:30 (English)
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Available from: 2025-01-30 Created: 2025-01-14 Last updated: 2025-01-23Bibliographically approved

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Bermejo-López, AitorKong, Wei-JunTortajada, Pedro JesusPosevins, DanielsMartín‐Matute, BelénBäckvall, Jan-E.

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