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Green Chemistry in Chemical Education and Synthetic Applications of Sulfinamides
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Organic chemistry.
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The preparation of chiral molecules, i.e. compounds that are not identical to their mirror image, is of great interest in the field of organic chemistry. The preparation of a enantiomerically pure molecules is crucial in the development of new pharmaceuticals, agrochemicals and more, since the building blocks of life are chiral and the interactions between enantiomers and receptor are different. Furthermore, an important aspect of chemistry is sustainability, developing new synthetic procedures where green chemistry has been incorporated.

In chapter 2, the use of Brønsted acid catalysis as well as a combined Brønsted acid and aminocatalytic procedure for the preparation of the chiral synthon tert-butane N-sulfinyl imine. Using HBF4•DEE as a catalyst gave the sulfinylimine in high yields in 2 h. Changing the catalyst to HBF4•DEE and aniline both improved the yields and shortened the reaction time to only 30 min. Furthermore, DFT-calculations were performed for both catalytic systems, providing a proposed mechanism suggesting a six-membered cyclic transition state as the key transition state.

In chapter 3 a light-assisted method for the preparation of chiral unnatural amino acids is presented. Via a photoredox-catalyzed decarboxylation of carboxylic acids, a carbon radical is generated that adds stereoselectively to an N-sulfinyl imine. This method allows for green synthesis of non-natural amino acids, and compared to previous methods, we have extended the radical source to include carboxylic acids.

In chapter 4, the use of green chemistry in B.Sc. level teaching is explored through an experimental design project for third-year students, using green chemistry as basis for analysis of literature procedures. Following this, the procedure is implemented in a first-year B.Sc. course. This is proven to be an efficient way to increase the students understanding of organic chemistry, as well as an efficient way to teach green chemistry.

Abstract [sv]

Framställandet av kirala molekyler är av stort intresse inom den organiska kemin. Framställandet av enantiomeriskt rena föreningar är av stort intresse när det gäller nya läkemedel, jordbrukskemikalier eller andra områden eftersom naturens byggstenar är kirala och interaktionen mellan enantiomerer och receptorer är olika. Vidare är hållbarhet en viktig aspekt inom kemin, utvecklandet av nya syntetiska procedurer med en analys baserad på grön kemi är därför av vikt.

I kapitel 2 användskatalytiskt, samt kombinationen av Brønsted syra och aminokatalys i framställandet av den kirala hjälpgruppen tert-butan N-sulfinyl iminen. HBF4 dietyleterat ger iminen på två timmar vid rumstemperatur. När det katalytiska systemet byts till kombinationen av HBF4 dietyleterat och anilin förbättrats utbytet efter 30 minuter. Vidare har DFT-beräkning utförts för båda de katalytiska systemen och en mekanism föreslagits. I slutet på kapitlet utvärderas metoderna baserat på grön kemi och syntetisk användbarhet, vidare presenteras en jämförelse med i litteraturen förekommande procedurer.

I kapitel 3 diskuteras en ljusaktiverad syntetisk metod för framställandet av kirala aminer. Genom fotoredox-katalyserad dekarboxylering genereras en kol-radikal som selektivt adderar till N-sulfinyliminen. Det här är en grön metod för framställandet av icke-naturliga aminosyror, där vi, jämfört med tidigare procedurer, har utökat de radikalkällor som kan användas till karboxylsyror.

I kapitel 4 utforskas grön kemi i utbildning på kandidat-nivå genom ett projekt i experimentdesign för tredjeårs studenter med de 12 principerna för grön kemi som utgångspunkt för analys och modifikationer. Den utvecklade proceduren implementerades sedan i en första-års kurs i organisk kemi där studenterna utför experimenten och diskuterar grön kemi. Detta har visat sig vara ett effektivt sätt att både öka förståelse och intresse för organisk kemi, så väl som ett effektivt sätt att lära studenter om vikten av grön kemi.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2020. , p. 45
Series
TRITA-CBH-FOU ; 2020:1
Keywords [en]
Sulfinamide, Green Chemistry, Chiral Auxiliary, Photoredox, Teaching
Keywords [sv]
Sulfinamid, Grön Kemi, Kiral Hjälpgrupp, Fotoredox, Undervisning
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-264910ISBN: 978-91-7873-400-9 (print)OAI: oai:DiVA.org:kth-264910DiVA, id: diva2:1375280
Public defence
2020-01-24, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20191217

Available from: 2019-12-17 Created: 2019-12-04 Last updated: 2019-12-17Bibliographically approved
List of papers
1. HBF4 center dot DEE-catalyzed formation of sulfinyl imines: Synthesis and mechanistic studies
Open this publication in new window or tab >>HBF4 center dot DEE-catalyzed formation of sulfinyl imines: Synthesis and mechanistic studies
2018 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 59, no 13, p. 1249-1253Article in journal (Refereed) Published
Abstract [en]

A mild acid-catalysed method is reported for the formation of sulfinyl imines from tert-butanesulfinamide and aromatic or aliphatic aldehydes using tetrafluoroboric acid diethyletherate (10 mol%) in dichloromethane. Reactions were performed at room temperature and gave the corresponding sulfinyl imines in excellent yield after 2 h. A DFT study was performed and a mechanism for the reaction is postulated. 

Place, publisher, year, edition, pages
PERGAMON-ELSEVIER SCIENCE LTD, 2018
Keywords
Sulfinyl imine, Bronsted acid catalysis, Tetrafluoroboric acid, Mechanistic study, DFT
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-225705 (URN)10.1016/j.tetlet.2018.02.051 (DOI)000428007300020 ()2-s2.0-85042402317 (Scopus ID)
Note

QC 20180411, Funding Agency: KTH-Royal Institute of Technology 

Available from: 2018-04-11 Created: 2018-04-11 Last updated: 2020-02-18Bibliographically approved
2. Mild and Rapid Aniline/HBF4 center dot DEE-Catalysed Formation of Sulfinyl Imines
Open this publication in new window or tab >>Mild and Rapid Aniline/HBF4 center dot DEE-Catalysed Formation of Sulfinyl Imines
2019 (English)In: ChemistrySelect, ISSN 2365-6549, Vol. 4, no 25, p. 7431-7436Article in journal (Refereed) Published
Abstract [en]

The combination of anline and tetrafluoroboric acid diethyl etherate (2.5 mol% and 5 mol%, respectively) significantly accelerates the formation of sulfinyl imines in dichloromethane and isopropylacetate at room temperature compared to previous procedures. A DFT and NMR spectroscopic study shows that the anilinium tetrafluoroborate complex is solvated by sulfinamide molecules in the initial state and that the rate-limiting step of the reaction is the addition of the sulfinamide molecule to the protonated aniline-based imine. In addition, the catalytic system was also utilised in a one-pot, two step reaction, where the in situ formed sulfinyl imine was arylated in a rhodium catalysed reaction with high diastereoselectivity.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2019
Keywords
Sulfinylimines, Organic synthesis, Organocatalysis, DFT, NMR
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-255378 (URN)10.1002/slct.201901218 (DOI)000474296800005 ()2-s2.0-85068481356 (Scopus ID)
Note

QC 20190730

Available from: 2019-07-30 Created: 2019-07-30 Last updated: 2019-12-16Bibliographically approved
3. Stereoselective Synthesis of Unnatural α-Amino Acids Through Visible Light-Promoted Decarboxylative C-Radical Addition to a Glyoxylate-Derived Sulfinyl Imine
Open this publication in new window or tab >>Stereoselective Synthesis of Unnatural α-Amino Acids Through Visible Light-Promoted Decarboxylative C-Radical Addition to a Glyoxylate-Derived Sulfinyl Imine
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-264908 (URN)
Note

QC 20191209

Available from: 2019-12-04 Created: 2019-12-04 Last updated: 2019-12-09Bibliographically approved
4. Student-Driven Development of Greener Chemistry in Undergraduate Teaching: Synthesis of Lidocaine Revisited
Open this publication in new window or tab >>Student-Driven Development of Greener Chemistry in Undergraduate Teaching: Synthesis of Lidocaine Revisited
Show others...
2019 (English)In: Journal of Chemical Education, ISSN 0021-9584, E-ISSN 1938-1328Article in journal (Refereed) Published
Abstract [en]

Green chemistry and sustainable development have become increasingly important topics for the education of future chemists, but the implementation of green chemistry into the chemistry curriculum requires significant efforts from teachers, especially in laboratory education. A student-driven development of a greener synthesis of Lidocaine was performed by three first-cycle, third-year students as a part of their B. Sc. degree project with the goal to implement the procedure in an under-graduate organic chemistry course. The students were merely provided with the framework for the project and were given the opportunity to independently develop the project based on an analysis of the 12 principles of green chemistry. The "greenification" of the Lidocaine synthesis by the three students led to several green improvements of the standard procedure, for example, (1) decreased reaction temperature, (2) solvent replacement, (3) fewer equivalents of the starting material (diethylamine) by the use of an inorganic bulk base, (4) use of catalytic amounts of potassium iodide to promote the Finkelstein reaction, and (5) a two-step one-pot procedure. Furthermore, one of the developed procedures was successfully implemented in a full-scale organic chemistry laboratory course.

National Category
Organic Chemistry Educational Sciences
Identifiers
urn:nbn:se:kth:diva-264909 (URN)10.1021/acs.jchemed.8b00567 (DOI)2-s2.0-85066912738 (Scopus ID)
Note

QC 20191209

Available from: 2019-12-04 Created: 2019-12-04 Last updated: 2020-03-05Bibliographically approved

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