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Direct Regiospecific and Highly Enantioselective Intermolecular α-Allylic Alkylation of Aldehydes By Combination of Transition Metal and amine Catalysts
Mid Sweden University, Faculty of Science, Technology and Media, Department of applied science and design.ORCID iD: 0000-0002-5108-6487
Mid Sweden University, Faculty of Science, Technology and Media, Department of applied science and design.
Mid Sweden University, Faculty of Science, Technology and Media, Department of applied science and design.
Mid Sweden University, Faculty of Science, Technology and Media, Department of applied science and design.
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2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 10, p. 2972-2977Article 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.

Place, publisher, year, edition, pages
2012. Vol. 18, no 10, p. 2972-2977
Keyword [en]
aldehydes; allylation; asymmetric catalysis; co-catalysis; transition metals
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:miun:diva-14579DOI: 10.1002/chem.201103366ISI: 000300837100028Scopus ID: 2-s2.0-84857544234OAI: oai:DiVA.org:miun-14579DiVA, id: diva2:446030
Available from: 2011-10-05 Created: 2011-10-05 Last updated: 2017-12-08Bibliographically approved
In thesis
1. Development of highly enantioselective organocatalyzed transformations
Open this publication in new window or tab >>Development of highly enantioselective organocatalyzed transformations
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University, 2011. p. 48
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 117
Keyword
Asymetric catalysis, aldehydes, proline derivatives, transition metals, Friedel-Crafts, conjugate addition, boration, α-alkylation
National Category
Organic Chemistry
Identifiers
urn:nbn:se:miun:diva-15621 (URN)978-91-86694-61-6 (ISBN)
Supervisors
Available from: 2011-12-22 Created: 2011-12-22 Last updated: 2012-07-30Bibliographically approved
2. Development of catalytic enantioselective C-C bond-forming and cascade transformations by merging homogeneous or heterogeneous transition metal catalysis with asymmetric aminocatalysis
Open this publication in new window or tab >>Development of catalytic enantioselective C-C bond-forming and cascade transformations by merging homogeneous or heterogeneous transition metal catalysis with asymmetric aminocatalysis
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. p. 70
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 206
Keyword
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:nbn:se:miun:diva-23605 (URN)978-91-87557-90-3 (ISBN)
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

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