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A bottom up approach towards artificial oxygenases by combining iron coordination complexes and peptides

Supramolecular systems resulting from the combination of peptides and a chiral iron coordination complex catalyze asymmetric epoxidation with aqueous hydrogen peroxide, providing good to excellent yields and high enantioselectivities in short reaction times. The peptide is shown to play a dual role; the terminal carboxylic acid assists the iron center in the efficient H 2 O 2 activation step, while its β-turn structure is crucial to induce high enantioselectivity in the oxygen delivering step. The high level of stereoselection (84-92% ee) obtained by these supramolecular catalysts in the epoxidation of 1,1′-alkyl ortho-substituted styrenes, a notoriously challenging class of substrates for asymmetric catalysis, is not attainable with any other epoxidation methodology described so far. The current work, combining an iron center ligated to N and O based ligands, and a peptide scaffold that shapes the second coordination sphere, may be seen as a bott om up approach towards the design of artificial oxygenases

MC acknowledge nancial support from MINECO of Spain and Fondo Europeo de Desarrollo Regional (CTQ2015-70795-P/ BQU), and the Catalan Department for Innovation, Universities and Enterprise (DIUE) of the Generalitat de Catalunya (2009SGR637).

Chemical Science, 2017, vol. 8, p. 3660-3667

Royal Society of Chemistry (RSC)

Author: Cussó Forest, Olaf
Giuliano, Michael W.
Ribas Salamaña, Xavi
Miller, Scott J.
Costas Salgueiro, Miquel
Date: 2017 January 1
Abstract: Supramolecular systems resulting from the combination of peptides and a chiral iron coordination complex catalyze asymmetric epoxidation with aqueous hydrogen peroxide, providing good to excellent yields and high enantioselectivities in short reaction times. The peptide is shown to play a dual role; the terminal carboxylic acid assists the iron center in the efficient H 2 O 2 activation step, while its β-turn structure is crucial to induce high enantioselectivity in the oxygen delivering step. The high level of stereoselection (84-92% ee) obtained by these supramolecular catalysts in the epoxidation of 1,1′-alkyl ortho-substituted styrenes, a notoriously challenging class of substrates for asymmetric catalysis, is not attainable with any other epoxidation methodology described so far. The current work, combining an iron center ligated to N and O based ligands, and a peptide scaffold that shapes the second coordination sphere, may be seen as a bott om up approach towards the design of artificial oxygenases
MC acknowledge nancial support from MINECO of Spain and Fondo Europeo de Desarrollo Regional (CTQ2015-70795-P/ BQU), and the Catalan Department for Innovation, Universities and Enterprise (DIUE) of the Generalitat de Catalunya (2009SGR637).
Format: application/pdf
Citation: https://doi.org/10.1039/C7SC00099E
ISSN: 2041-6520 (versió paper)
2041-6539 (versuó electrònica)
Document access: http://hdl.handle.net/10256/14495
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MINECO/PE 2016-2018/CTQ2015-70795-P
Reproducció digital del document publicat a: https://doi.org/10.1039/C7SC00099E
Articles publicats (D-Q)
Is part of: Chemical Science, 2017, vol. 8, p. 3660-3667
Rights: Attribution-NonCommercial 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by-nc/3.0/es/
Subject: Oxigenases
Oxygenases
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Title: A bottom up approach towards artificial oxygenases by combining iron coordination complexes and peptides
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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