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Advances in Sustainable Catalytic Transformations for Organic Synthesis
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-5212-8255
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 [en]
Catalysis, Sustainability, Photochemistry, Electrochemistry, Organic Synthesis, Cellulose
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-237931ISBN: 978-91-8107-078-1 (print)ISBN: 978-91-8107-079-8 (electronic)OAI: oai:DiVA.org:su-237931DiVA, id: diva2:1927447
Public defence
2025-02-24, Magneli Salen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16B, Stockholm, 09:30 (English)
Opponent
Supervisors
Available from: 2025-01-30 Created: 2025-01-14 Last updated: 2025-01-23Bibliographically approved
List of papers
1. Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates
Open this publication in new window or tab >>Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates
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2023 (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. 

Keywords
Allenes, allenylboronates, borylation, iron, propargyl esters
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-213118 (URN)10.1002/chem.202203130 (DOI)000888153700001 ()36250587 (PubMedID)2-s2.0-85143203381 (Scopus ID)
Available from: 2022-12-20 Created: 2022-12-20 Last updated: 2025-01-14Bibliographically approved
2. Selective Synthesis of Imines by Photo-Oxidative Amine Cross-Condensation Catalyzed by PCN-222(Pd)
Open this publication in new window or tab >>Selective Synthesis of Imines by Photo-Oxidative Amine Cross-Condensation Catalyzed by PCN-222(Pd)
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2021 (English)In: ACS Sustainable Chemistry and Engineering, E-ISSN 2168-0485, Vol. 9, no 43, p. 14405-14415Article in journal (Refereed) Published
Abstract [en]

Palladium-metalated PCN-222 enables the aerobic photo-oxidative cross-condensation of anilines with benzylic amines yielding a series of linear and cyclic imines. The reaction is very efficient under mild conditions, which allows the isolation of simple, yet elusive, intermediates such as 2-(benzylideneamino)-aniline and 2-(benzylideneamino)phenols. Recyclability studies show excellent activity and selectivity after five runs. The methodology was successfully applied for the synthesis of an antitumor agent (PMX-610).

Keywords
imines, photoredox, MOF, recyclability, heterogeneous catalysis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-199558 (URN)10.1021/acssuschemeng.1c04389 (DOI)000715216700010 ()
Available from: 2021-12-13 Created: 2021-12-13 Last updated: 2025-01-14Bibliographically approved
3. A Cellulose-based Heterogeneous Ru/BINAP Catalyst for Sustainable Asymmetric Hydrogenation of Alkenes
Open this publication in new window or tab >>A Cellulose-based Heterogeneous Ru/BINAP Catalyst for Sustainable Asymmetric Hydrogenation of Alkenes
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) is one of the most widely used chiral ligands for the synthesis of enantioenriched compounds, both on laboratory and industrial scales. The immobilization of such ligands on recyclable materials can significantly enhance the economic efficiency and sustainability of these transformations. Herein, we report the successful immobilization of BINAP on microcrystalline cellulose (MCC) and its application in the asymmetric hydrogenation of α,β-unsaturated carboxylic acids. This approach represents the first example of heterogeneous asymmetric hydrogenation of aliphatic α,β-unsaturated carboxylic acids. Moreover, the use of MCC as an environmentally benign and cost-effective heterogeneous support underscores its potential for promoting sustainability in catalytic processes.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-237934 (URN)
Available from: 2025-01-14 Created: 2025-01-14 Last updated: 2025-01-14
4. Electrochemical hydrogenation of alkenes over a nickel foam guided by life cycle, safety and toxicological assessments
Open this publication in new window or tab >>Electrochemical hydrogenation of alkenes over a nickel foam guided by life cycle, safety and toxicological assessments
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2025 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 27, no 1, p. 227-239Article in journal (Refereed) Published
Abstract [en]

The electrochemical hydrogenation of enones and alkenes using commercial nickel foam and an aqueous acidic solution is presented. The reaction shows excellent selectivity in C C vs. C O reduction, with enhanced activity when using 7% of nBuOH as cosolvent. The method presents good applicability and recyclability properties, with more than 30 different substrates explored, and it can be recycled at least 15 times. Toxicological and screening life cycle assessments were used to identify potential “hotspots” of environmental and human health impact during the development phase of the method, as well as to evaluate the performance of the electrochemical nickel method against the conventional use of Pd/C and H2 gas.

National Category
Natural Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-237929 (URN)10.1039/d4gc02924k (DOI)
Funder
Mistra - The Swedish Foundation for Strategic Environmental Research, 2018/11Swedish Research Council
Available from: 2025-01-14 Created: 2025-01-14 Last updated: 2025-02-13Bibliographically approved

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Tortajada, Pedro J.

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