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Highly Enantioselective Cascade Transformations by Merging Heterogeneous Transition Metal Catalysis with Asymmetric Aminocatalysis
Univ Stockholm, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden . (Armando Córdova)
Mittuniversitetet, Fakulteten för naturvetenskap, teknik och medier, Institutionen för tillämpad naturvetenskap och design. (Armando Córdova)ORCID-id: 0000-0002-5108-6487
Univ Stockholm, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden . (Armando Córdova)
Univ Stockholm, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden .
Vise andre og tillknytning
2012 (engelsk)Inngår i: Scientific reports, ISSN 2045-2322, Vol. 2, s. Art. no. 851-Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2012. Vol. 2, s. Art. no. 851-
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Identifikatorer
URN: urn:nbn:se:miun:diva-18080DOI: 10.1038/srep00851ISI: 000311100900004Scopus ID: 2-s2.0-84870851921OAI: oai:DiVA.org:miun-18080DiVA, id: diva2:580131
Tilgjengelig fra: 2012-12-20 Laget: 2012-12-20 Sist oppdatert: 2016-10-17bibliografisk kontrollert
Inngår i avhandling
1. Development of catalytic enantioselective C-C bond-forming and cascade transformations by merging homogeneous or heterogeneous transition metal catalysis with asymmetric aminocatalysis
Åpne denne publikasjonen i ny fane eller vindu >>Development of catalytic enantioselective C-C bond-forming and cascade transformations by merging homogeneous or heterogeneous transition metal catalysis with asymmetric aminocatalysis
2014 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Sundsvall: Mid Sweden University, 2014. s. 70
Serie
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 206
Emneord
asymmetric catalysis, transition metals, aldehydes, heterogeneous catalysis, amino acid, organocatalysis, α-allylation, β-alkylation, dynamic transformations, polysubstituted, carbocycles, spirocyclic oxindoles, all-carbon quaternary stereocenters
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Identifikatorer
urn:nbn:se:miun:diva-23605 (URN)978-91-87557-90-3 (ISBN)
Disputas
2014-10-24, 10:15 (engelsk)
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Veileder
Tilgjengelig fra: 2014-12-05 Laget: 2014-12-05 Sist oppdatert: 2016-09-29bibliografisk kontrollert

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