Functional models of oxygenases

Functional models of non-heme Cu, Mn and Fe oxygenases

Researcher in charge: Miquel Costas

In this research line selective oxidation of C-H and C=C bonds is targeted in this research line via design of iron and manganese catalysts inspired in the active site of non-heme oxygenases, which could operate via activation of oxidants with high atom efficiency and low environmental impact. Elements to control regio, chemo and stereoselectivity are investigated. Selectivity is pursued via rational design of catalysts that exploit substrate recognition-exclusion phenomena, and control over proton and electron affinity of the active species. The fundamental mechanistic aspects are also studied with the aim of designing the catalysts of the future, and understanding the chemistry taking place in non-heme iron and manganese-dependent oxygenases. Fundamental basis to control formation of the O-O bond via oxidation of the water molecule by well-defined high valent metal-oxo species is also pursued.
An additional goal of is to prepare and characterize non porphyrinic iron and manganese complexes with high oxidation states. Understanding the chemistry of high valent metal-oxo species is fundamentally interesting because of their relevance in biology and in challenging catalytic oxidation reactions including C-H hydroxylation and O-O bond formation.

Art 61

Selected publications:

The Iron(II) Complex [Fe(CF3SO3)2(mcp)] as a Convenient, Readily Available Catalyst for the Selective Oxidation of Methylenic Sites in Alkanes”
Mercè Canta, David Font, Laura Gómez, Xavi Ribas, Miquel Costas*
Adv. Synth. Catal. 2014356, 818-830. DOI: 10.1002/adsc.201300923

“Selective Ortho-Hydroxylation–Defluorination of 2-Fluorophenolates with a Bis(μ-oxo)dicopper(III) Species”
Joan Serrano-Plana, Isaac Garcia-Bosch, Ryosuke Miyake, Miquel Costas,* Anna Company*
Angew. Chem. Int. Ed. 201453, 9608–9612. DOI: 10.1002/anie.201405060

“Regioselective Oxidation of Nonactivated Alkyl C−H Groups Using Highly Structured Non-Heme Iron Catalysts”
Laura Gómez, Mercè Canta, David Font, Irene Prat, Xavi Ribas, Miquel Costas*
J. Org. Chem. 2013, 78, 1421-1433. DOI: 10.1021/jo302196q

“Highly Stereoselective Epoxidation with H2OCatalyzed by Electron-Rich Aminopyridine Manganese Catalysts”
Olaf Cussó, Isaac Garcia-Bosch, David Font, Xavi Ribas, Julio Lloret-Fillol, Miquel Costas*
J. Am. Chem. Soc. 201315, 6158-6161. DOI: 10.1021/ol403018x