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Development of Catalytic Enantioselective Approaches for the Synthesis of Carbocycles and Heterocycles
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In biological systems, most of the active organic molecules are chiral. Some of the main constituents of living organisms are amino acids and sugars. They exist predominantly in only one enantiomerically pure form. For example, our proteins are built-up by L-amino acids and as a consequence they are enatiomerically pure and will interact in different ways with enantiomers of chiral molecules. Indeed, different enantiomers or diastereomers of a molecule could often have a drastically different biological activity. It is of paramount importance in organic synthesis to develop new routes to control and direct the stereochemical outcome of reactions. The aim of this thesis is to investigate new protocols for the synthesis of complex chiral molecules using simple, environmentally friendly proline-based organocatalysts. We have investigated, the aziridination of linear and branched enals, the stereoselective synthesis of β-amino acids with a carbene co-catalyst, the synthesis of pyrazolidines, the combination of heterogeneous transition metal catalysis and amine catalysis to deliver cyclopentenes bearing an all-carbon quaternary stereocenter and a new heterogeneous dual catalyst system for the carbocyclization of enals. The reactions presented in this thesis afforded the corresponding products with high levels of chemo-, diastero- and enantioselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2013. , 75 p.
Keyword [en]
Organocatalysis, Asymmetric Catalysis, Heterogeneous Catalysis, Aziridines, Pyrazolidines, Cyclopentanes
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-94680ISBN: 978-91-7447-781-8 (print)OAI: oai:DiVA.org:su-94680DiVA: diva2:659183
Public defence
2013-12-04, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Submitted. 

Available from: 2013-11-12 Created: 2013-10-08 Last updated: 2014-09-24Bibliographically approved
List of papers
1. Catalytic asymmetric aziridination of α,β-unsaturated aldehydes
Open this publication in new window or tab >>Catalytic asymmetric aziridination of α,β-unsaturated aldehydes
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2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 28, 7904-7917 p.Article in journal (Refereed) Published
Abstract [en]

The development, scope, and application of the highly enantioselective organocatalytic aziridination of α,β-unsaturated aldehydes is presented. The aminocatalytic azirdination of α,β-unsaturated aldehydes enables the asymmetric formation of β-formyl aziridines with up to >19:1 d.r. and 99% ee. The aminocatalytic aziridination of α-monosubstituted enals gives access to terminal α-substituted-α-formyl aziridines in high yields and upto 99% ee. In the case of the organocatalytic aziridination of disubstituted α,β-unsaturated aldehydes, the transformations were highly diastereo- and enantioselective and give nearly enantiomerically pure β-formyl-functionalized aziridine products (99% ee). A highly enantioselective one-pot cascade sequence based on the combination of asymmetric amine and N-heterocycliccarbene catalysis (AHCC) is also disclosed. This one-pot three-component co-catalytic transformation between α,β-unsaturated aldehydes, hydroxylamine derivatives, and alcohols gives the corresponding N-tert-butoxycarbonyl and N-carbobenzyloxy-protected β-amino acid esters with ee values ranging from 92–99%. The mechanisms and stereochemistry of all these catalytic transformations are also discussed.

Keyword
asymmetric catalysisaziridines, domino reactions, hydroxylamines, unsaturated aldehydes
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-61949 (URN)10.1002/chem.201100042 (DOI)000293383300028 ()
Funder
Swedish Research Council
Available from: 2011-09-06 Created: 2011-09-06 Last updated: 2017-12-08Bibliographically approved
2. Organocatalytic enantioselective aziridination of α-substituted α,β-unsaturated aldehydes: asymmetric synthesis ot terminal aziridines
Open this publication in new window or tab >>Organocatalytic enantioselective aziridination of α-substituted α,β-unsaturated aldehydes: asymmetric synthesis ot terminal aziridines
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2010 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 352, no 18, 3201-3207 p.Article in journal (Refereed) Published
Abstract [en]

The first example of a highly enantioselective organocatalytic aziridination of α-substituted α,β-unsaturated aldehydes is presented. The reaction is catalyzed by simple chiral amines and gives access to highly functional terminal azirdines containing an α-tertiary amine stereocenter in high yields and enantiomeric ratios (95.5:4.5–98:2).

Keyword
asymmetric catalysis, domino reactions, organocatalysis, α-substituted α, β-unsaturated aldehydes, terminal aziridines
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-52926 (URN)10.1002/adsc.201000650 (DOI)
Funder
Swedish Research Council
Available from: 2011-01-19 Created: 2011-01-19 Last updated: 2017-12-11Bibliographically approved
3. Direct Catalytic Asymmetric Synthesis of Pyrazolidine Derivatives
Open this publication in new window or tab >>Direct Catalytic Asymmetric Synthesis of Pyrazolidine Derivatives
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2012 (English)In: ChemistryOpen, ISSN 2191-1363, Vol. 1, no 3, 134-139 p.Article in journal (Refereed) Published
Abstract [en]

A highly enantioselective, metal-free cascade reaction between di-1,2-N-protected hydrazine and α,β-unsaturated aldehydes is disclosed. The catalytic, asymmetric cascade transformation is a direct entry to 3-hydroxypyrazolidine and 3-allylpyrazolidine derivatives in one step and two steps, respectively, with >19:1 d.r. and 98–99 % ee using simple chiral pyrrolidines as catalysts.

Keyword
1, 4-selectivity, asymmetric catalysis, cascade reactions, hemiaminals, metal-free catalysis, pyrazolidines
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-94675 (URN)10.1002/open.201200015 (DOI)
Available from: 2013-10-08 Created: 2013-10-08 Last updated: 2017-12-06Bibliographically approved
4. Highly Enantioselective Cascade Transformations by Merging Heterogeneous Transition Metal Catalysis with Asymmetric Aminocatalysis
Open this publication in new window or tab >>Highly Enantioselective Cascade Transformations by Merging Heterogeneous Transition Metal Catalysis with Asymmetric Aminocatalysis
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2012 (English)In: Scientific Reports, ISSN 2045-2322, E-ISSN 2045-2322, Vol. 2, 851- p.Article in journal (Refereed) Published
Abstract [en]

The concept of combining heterogeneous transition metal and amine catalysis for enantioselective cascade reactions has not yet been realized. This is of great advantage since it would allow for the recycling of expensive and non-environmentally friendly transition metals. We disclose that the use of a heterogeneous Pd-catalyst in combination with a simple chiral amine co-catalyst allows for highly enantioselective cascade transformations. The preparative power of this process has been demonstrated in the context of asymmetric cascade Michael/carbocyclization transformations that delivers cyclopentenes bearing an all carbon quaternary stereocenters in high yields with up to 30: 1 dr and 99% ee. Moreover, a variety of highly enantioselective cascade hetero-Michael/carbocyclizations were developed for the one-pot synthesis of valuable dihydrofurans and pyrrolidines (up to 98% ee) by using bench-stable heterogeneous Pd and chiral amines as co-catalysts.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-83802 (URN)10.1038/srep00851 (DOI)000311100900004 ()
Funder
Swedish Research Council
Note

AuthorCount:6;

Available from: 2012-12-14 Created: 2012-12-14 Last updated: 2017-12-06Bibliographically approved
5. Enantioselective Heterogeneous Synergistic Catalysis for Asymmetric Cascade Transformations
Open this publication in new window or tab >>Enantioselective Heterogeneous Synergistic Catalysis for Asymmetric Cascade Transformations
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2014 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 356, no 11-12, 2485-2492 p.Article in journal (Refereed) Published
Abstract [en]

A modular design for a novel heterogeneous synergistic catalytic system, which simultaneously activates the electrophile and nucleophile by the combined activation modes of a separate metal and non-metal catalyst, for asymmetric cascade transformations on a solid surface is disclosed. This modular catalysis strategy generates carbocycles (up to 97.5: 2.5 er) as well as spirocyclic oxindoles (97.5: 2.5 to > 99: 0.5 er), containing all-carbon quaternary centers, in a highly enantioselective fashion via a one-pot dynamic relay process.

Keyword
all-carbon quaternary stereocenters, carbocycles, co-catalysis, dynamic transformations, heterogeneous synergistic catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-107625 (URN)10.1002/adsc.201400291 (DOI)000340567100014 ()
Funder
Swedish Research CouncilVINNOVA
Note

AuthorCount:8;

Available from: 2014-09-24 Created: 2014-09-22 Last updated: 2017-12-05Bibliographically approved

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