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Publications

van Berkel, S. S.; Bögels, B. G. M.; Wijdeven, M. A.; Westermann, B.; Rutjes, F. P. J. T.; Recent Advances in Asymmetric Isocyanide-Based Multicomponent Reactions Eur. J. Org. Chem. 2012 3543-3559 (2012) DOI: 10.1002/ejoc.201200030
  • Abstract
  • BibText
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This review discusses the use of various isocyanides (regular, chiral, and convertible) in asymmetric multicomponent reactions. In particular, stereoselective Ugi and Passerini reactions are highlighted, as well as their applications in modular sequential reactions and natural product synthesis.Isocyanide‐based multicomponent reactions (IMCRs) can be considered one of the breakthrough reaction classes of the last century. Moreover, asymmetric IMCRs have recently developed into powerful reactions for the versatile synthesis of highly complex molecules. The progress made in the development of stereoselective Passerini and Ugi reactions has led to the advancement of catalytic asymmetric IMCRs. This review gives an overview of recent advances in the field of asymmetric IMCRs with a focus on stereoselective α‐additions of isocyanides. In addition, the use of convertible isocyanides in stereoselective cascade IMCRs is covered and future opportunities and potential applications of (asymmetric) IMCRs are briefly discussed.

Publications

Eschen-Lippold, L.; Rosahl, S.; Westermann, B.; Arnold, N.; Aus Pilzen isolierte Substanz gegen den Erreger der Kraut- und Knollenfäule Kartoffelbau 63 18-21 (2012)
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Publications

Brauch, S.; Henze, M.; Osswald, B.; Naumann, K.; Wessjohann, L. A.; van Berkel, S. S.; Westermann, B.; Fast and efficient MCR-based synthesis of clickable rhodamine tags for protein profiling Org. Biomol. Chem. 10 958-965 (2012) DOI: 10.1039/C1OB06581E
  • Abstract
  • BibText
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Protein profiling probes are important tools for studying the composition of the proteome and as such have contributed greatly to the understanding of various complex biological processes in higher organisms. For this purpose the application of fluorescently labeled activity or affinity probes is highly desirable. Especially for in vivodetection of low abundant target proteins, otherwise difficult to analyse by standard blotting techniques, fluorescently labeled profiling probes are of high value. Here, a one-pot protocol for the synthesis of activated fluorescent labels (i.e.azide, alkynyl or NHS), based on the Ugi-4-component reaction (Ugi-4CR), is presented. As a result of the peptoidic structure formed, the fluorescent properties of the products are pH insensitive. Moreover, the applicability of these probes, as exemplified by the labeling of model protein BSA, will be discussed.

Publications

Neves Filho, R. A. W.; Westermann, B.; Wessjohann, L. A.; Synthesis of (−)-julocrotine and a diversity oriented Ugi-approach to analogues and probes Beilstein J. Org. Chem. 7 1504-1507 (2011) DOI: 10.3762/bjoc.7.175
  • Abstract
  • BibText
  • RIS

An improved total synthesis of (−)-julocrotine in three steps from Cbz-glutamine, in 51% overall yield, is presented. To demonstrate the potential of the heterocyclic moiety for diversity oriented synthesis, a series of (−)-julocrotine analogues was synthesized by employing the heterocyclic precursor as an amino input in Ugi four-component reactions (Ugi-4CR) [1].

Publications

Nawaz, S. A.; Ayaz, M.; Brandt, W.; Wessjohann, L. A.; Westermann, B.; Cation–π and π–π stacking interactions allow selective inhibition of butyrylcholinesterase by modified quinine and cinchonidine alkaloids Biochem. Biophys. Res. Commun. 404 935-940 (2011) DOI: 10.1016/j.bbrc.2010.12.084
  • Abstract
  • BibText
  • RIS

Scaffold varied quaternized quinine and cinchonidine alkaloid derivatives were evaluated for their selective butyrylcholinesterase (BChE) inhibitory potential. Ki values were between 0.4–260.5 μM (non-competitive inhibition) while corresponding Kivalues to acetylcholinesterase (AChE) ranged from 7.0–400 μM exhibiting a 250-fold selectivity for BChE.Docking arrangements (GOLD, PLANT) revealed that the extended aromatic moieties and the quaternized nitrogen of the inhibitors were responsible for specific π–π stacking and π–cation interactions with the choline binding site and the peripheral anionic site of BChE’s active site.

Publications

Dubberke, S.; Abbas, M.; Westermann, B.; Oxidative allylic rearrangement of cycloalkenols: Formal total synthesis of enantiomerically pure trisporic acid B Beilstein J. Org. Chem. 7 421-425 (2011) DOI: 10.3762/bjoc.7.54
  • Abstract
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  • RIS

Enantiomerically highly enriched unsaturated β-ketoesters bearing a quaternary stereocenter can be utilized as building blocks for the synthesis of natural occurring terpenes, i. a., trisporic acid and its derivatives. An advanced building block has been synthesized in a short reaction sequence, which involves an oxidative allylic rearrangement initiated by pyridinium dichromate (PDC) as the key step.

Publications

Westermann, B.; Ayaz, M.; van Berkel, S.; Enantiodivergente Organokaskadenreaktionen Angew. Chem. 122 858-861 (2010) DOI: 10.1002/ange.200904638
  • Abstract
  • BibText
  • RIS

In der Synthese strukturell und stereochemisch komplexer Moleküle mithilfe von Organokaskadenreaktionen können Katalysatoren auf enantiodivergente Weise wirken. Ein Beispiel ist der asymmetrische Aufbau quartärer Kohlenstoffzentren über komplementäre Enamin/Iminium‐Katalysen (siehe Schema; En=Enaminaktivierung, Im=Iminiumaktivierung).

Publications

Westermann, B.; Ayaz, M.; van Berkel, S.; Enantiodivergent Organocascade Reactions Angew. Chem. Int. Ed. 49 846-849 (2010) DOI: 10.1002/anie.200904638
  • Abstract
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By targeting structural and stereochemical complexity with organocascade reactions, distinct catalysts can form molecular frameworks in an enantiodivergent way. This goal was elegantly achieved for the asymmetric synthesis of quaternary carbon centers by two complementary routes employing cascades of either enamine or iminium catalysis (see scheme; En=enamine activation, Im=iminium activation).

Publications

Henze, M.; Kreye, O.; Brauch, S.; Nitsche, C.; Naumann, K.; Wessjohann, L. A.; Westermann, B.; Photoaffinity-Labeled Peptoids and Depsipeptides by Multicomponent Reactions Synthesis 2010 2997-3003 (2010) DOI: 10.1055/s-0030-1258182
  • Abstract
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Photoaffinity tags can be incorporated easily into peptoids and congeners by the Ugi and Passerini multicomponent reactions. Products related to photo-methionine and photo-leucine can be accomplished by diazirine-containing building blocks. The same protocols can be used to synthesize derivatives with benzophenone photo cross-linkers.

Publications

Brauch, S.; Gabriel, L.; Westermann, B.; Seven-component reactions by sequential chemoselective Ugi–Mumm/Ugi–Smiles reactions Chem. Commun. 46 3387-3389 (2010) DOI: 10.1039/B927388C
  • Abstract
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A seven-component reaction was accomplished by utilizing the different chemoselectivities of the Ugi–Mumm and the Ugi–Smiles reaction. The sequential multicomponent reactions led to highly diverse peptide and glycopeptide like structures.

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