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Chem Sci. 2017 May 1;8(5):3660-3667. doi: 10.1039/C7SC00099E. Epub 2017 Mar 3.

A Bottom Up Approach Towards Artificial Oxygenases by Combining Iron Coordination Complexes and Peptides.

Author information

1
Institut de Química Computational i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona E-17071, Catalonia, Spain.
2
Department of Chemistry and Biochemistry, College of Charleston, South Carolina, United States.
3
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.

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 H2O2 activation step, while its β-turn structure is crucial to induce high enantioselectivity in the oxygen delivering step. The high levels of stereoselection (84-92% ee) obtained by these supramolecular catalysts in the epoxidation of 1,1'-alkyl orthosubstituted styrenes, a notoriously challenging class of substrates for asymmetric catalysis, are 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 bottom up approach towards the design of artificial oxygenases.

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