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Development of catalytic enantioselective C-C bond-forming and cascade transformations by merging homogeneous or heterogeneous transition metal catalysis with asymmetric aminocatalysis
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences. (Armando Córdova)ORCID iD: 0000-0002-5108-6487
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Chiral molecules play a central role in our daily life and in nature, for instance the different enantiomers or diastereomers of a chiral molecule may show completely different biological activity. For this reason, it is a vital goal for synthetic chemists to design selective and efficient methodologies that allow the synthesis of the desired enantiomer. In this context, it is highly important that the concept of green chemistry is considered while designing new approaches that eventually will provide more environmental and sustainable chemical synthesis.The aim of this thesis is to develop the concept of combining transition metal catalysis and aminocatalysis in one process (dual catalysis). This strategy would give access to powerful tools to promote reactions that were not successful with either transition metal catalyst or the organocatalyst alone. The protocols presented in this thesis based on organocatalytic transformations via enamine or iminium intermediates or both, in combination with transition metal catalysis, describes new enantioselective organocatalytic procedures that afford valuable compounds with high chemo- and enantioselectivity from inexpensive commercial available starting materials. In paper I, we present a successful example of dual catalysis: the combination of transition metal activation of an electrophile and aminocatalyst activation of a nucleophile via enamine intermediate. In paper II, the opposite scenario is presented, here the transition metal activates the nucleophile and the aminocatalyst activates the electrophile via an iminium intermediate. In paper III,we present a domino Michael/carbocyclisation reaction that is catalysed by a chiral amine (via iminium/enamine activation) in combination with a transition metal catalysts activation of an electrophile. In paper IV, the concept of dual catalysis was further extended and applied for the highly enantioselective synthesis of valuable structural scaffolds, namely poly-substituted spirocyclic oxindoles. Finally, in paper V the concept of dual catalysis was expanded, by investigating more challenging and environmentally benign processes, such as the successful combination of a heterogeneous palladium and amine catalysts for the highly enantioselective synthesis of functionalised cyclopentenes, containing an all carbonquaternary stereocenter, dihydrofurans and dihydropyrrolidines.

Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University , 2014. , 70 p.
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 206
Keyword [en]
asymmetric catalysis, transition metals, aldehydes, heterogeneous catalysis, amino acid, organocatalysis, α-allylation, β-alkylation, dynamic transformations, polysubstituted, carbocycles, spirocyclic oxindoles, all-carbon quaternary stereocenters
National Category
Natural Sciences Chemical Sciences
Identifiers
URN: urn:nbn:se:miun:diva-23605ISBN: 978-91-87557-90-3 (print)OAI: oai:DiVA.org:miun-23605DiVA: diva2:768971
Public defence
2014-10-24, 10:15 (English)
Opponent
Supervisors
Available from: 2014-12-05 Created: 2014-12-05 Last updated: 2016-09-29Bibliographically approved
List of papers
1. Direct Regiospecific and Highly Enantioselective Intermolecular α-Allylic Alkylation of Aldehydes By Combination of Transition Metal and amine Catalysts
Open this publication in new window or tab >>Direct Regiospecific and Highly Enantioselective Intermolecular α-Allylic Alkylation of Aldehydes By Combination of Transition Metal and amine Catalysts
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2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 10, 2972-2977 p.Article in journal (Refereed) Published
Abstract [en]

The first direct intermolecular regiospecific and highly enantioselective α-allylic alkylation of linear aldehydes by a combination of achiral bench-stable Pd 0 complexes and simple chiral amines as co-catalysts is disclosed. The co-catalytic asymmetric chemoselective and regiospecificα-allylic alkylation reaction is linked in tandem with in situ reduction to give the corresponding 2-alkyl alcohols with high enantiomeric ratios (up to 98:2 e.r.; e.r.=enantiomeric ratio). It is also an expeditious entry to valuable 2-alkyl substituted hemiacetals, 2-alkyl-butane-1,4-diols, and amines. The concise co-catalytic asymmetric total syntheses of biologically active natural products (e.g., Arundic acid) are disclosed. Go organic! Directintermolecular regiospecific and highly enantioselective α-allylic alkylation of linear aldehydes by a combination of achiral bench-stable Pd 0complexes and simple chiral amines as co-catalysts is disclosed (see scheme). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keyword
aldehydes; allylation; asymmetric catalysis; co-catalysis; transition metals
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-14579 (URN)10.1002/chem.201103366 (DOI)000300837100028 ()2-s2.0-84857544234 (Scopus ID)
Available from: 2011-10-05 Created: 2011-10-05 Last updated: 2016-09-29Bibliographically approved
2. Catalytic Enantioselective beta-Alkylation of alpha,beta-Unsaturated Aldehydes by Combination of Transition-Metal- and Aminocatalysis: Total Synthesis of Bisabolane Sesquiterpenes
Open this publication in new window or tab >>Catalytic Enantioselective beta-Alkylation of alpha,beta-Unsaturated Aldehydes by Combination of Transition-Metal- and Aminocatalysis: Total Synthesis of Bisabolane Sesquiterpenes
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2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 32, 8784-8788 p.Article in journal (Refereed) Published
Abstract [en]

Branching out! The first co-catalytic enantioselective (up to 98:2 e.r.) β-alkylation of α,β-unsaturated aldehydes by combination of simple chiral amine and copper catalysts provides β-branched aldehydes in a one-pot protocol (see scheme). The methodology was applied to the short total syntheses of bisabolane sesquiterpenes (S)-(+)-curcumene, (E)-(S)-(+)-3- dehydrocurcumene and (S)-(+)-tumerone. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keyword
aldehydes; alkylation; asymmetric conjugate additions; enantioselectivity; co-catalysis; zinc
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-14528 (URN)10.1002/chem.201100756 (DOI)000294704700003 ()2-s2.0-79960754105 (Scopus ID)
Available from: 2011-09-23 Created: 2011-09-23 Last updated: 2016-09-29Bibliographically approved
3. A palladium/chiral amine co-catalyzed enantioselective dynamic cascade reaction: Synthesis of polysubstituted carbocycles with a quaternary carbon stereocenter
Open this publication in new window or tab >>A palladium/chiral amine co-catalyzed enantioselective dynamic cascade reaction: Synthesis of polysubstituted carbocycles with a quaternary carbon stereocenter
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2013 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, no 23, 6050-6054 p.Article in journal (Refereed) Published
Abstract [en]

Polysubstituted 5- and 6-membered carbocycles were synthesized by the title reaction. The one-pot dynamic relay process generates four new stereocenters, including a quaternary carbon center, in a highly enantioselective fashion (99.5:0.5→99:0.5 e.r.) by using a simple combination of palladium and chiral amine co-catalysts. 

Keyword
aldehydes, asymmetric catalysis, carbocycles, co-catalysis, quaternary carbon stereocenters
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-19359 (URN)10.1002/anie.201300559 (DOI)000319742400028 ()2-s2.0-84878387915 (Scopus ID)
Note

:doi 10.1002/anie.201300559

Available from: 2013-09-05 Created: 2013-06-19 Last updated: 2016-09-29Bibliographically 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, Vol. 2, Art. no. 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 cascadetransformations. The preparative power of this process has been demonstrated in the context of asymmetric cascade Michael/carbocyclizationtransformations 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. © 2012 Macmillan Publishers Limited. All rights reserved.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-18080 (URN)10.1038/srep00851 (DOI)000311100900004 ()2-s2.0-84870851921 (Scopus ID)
Available from: 2012-12-20 Created: 2012-12-20 Last updated: 2016-10-17Bibliographically approved

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