Bio-inspired iron complexes for stereoselective oxidation reactions using hydrogen peroxide as the oxidant: a hydrogen bonding network to mimic the protein environment

• Research unit: COST
• Project number: C13.0038

Key words (English)

iron catalysis; bio-inspired chemistry; hydrogen bonding catalysis; asymmetric oxidation; hydrogen peroxide; homogeneous catalysis

Research programs (English)

COST-Action CM1003 - Biological oxidation reactions - mechanisms and design of new catalysts

Short description (English)

Hydrogen peroxide is one of the most green and desirable oxidants for oxidation reactions. Nature utilizes peroxidases to catalyze biological oxidation reactions utilizing H2O2. Bio-mimetic catalysts have not achieved the same efficiency as the enzymes. Herein we propose to develop iron catalysts inspired by both the primary and the secondary coordination spheres of iron-containing peroxidases and related monooxygenases. Specifically, we propose to develop anionic chiral pincer ligands incorporating nitrogen donors. Most importantly, the ligands contain hydrogen bond donors and acceptors which could serve as proton relays for the activation of H2O2. Iron complexes of these ligands will be synthesized, characterized, and applied for stereoselective oxidation reactions. We will focus on asymmetric oxidation of organic sulfides and epoxidation of olefins. The work will involve collaboration with multiple COST partners, particularly in the characterization of paramagnetic iron complexes and the mechanistic studies using both experimental and computational methods.

Further information (English)

Full name of research-institution/enterprise: EPF Lausanne Institut des sciences et ingénierie chimiques EPFL-SB-ISIC, LSCI, BCH 3305

Partners and International Organizations (English)

AT; CZ; DK; FI; FR; DE; HU; IE; IT; NL; NO; PL; PT; ES; SE; TR; UK

Abstract (English)

Hydrogen peroxide is one of the most green and désirable oxidants for oxidation reactions. Nature utilizes peroxidases to catalyze biological oxidation reactions utilizing H202. Bio-mimetic catalysts have not achieved the same efficiency as the enzymes. Herein we propose to develop iron catalysts inspired by both the primary and the secondary coordination sphères of iron-containing peroxidases and related monooxygenases. Specifically, we propose to develop anionic chiral pincer ligands incorporating nitrogen donors. Most importantly, the ligands contain hydrogen bond donors and acceptors which could serve as proton relays for the activation of H202. Iron complexes of thèse ligands will be synthesized, characterized, and applied for stereoselective oxidation reactions. We will focus on asymmetric oxidation of organic Sulfides and epoxidation of olefins. The wori< will involve collaboration with multiple COST partners, particularty in the characterization of paramagnetic iron complexes and the mechanistic studies using both expérimental and computational methods.

References in databases (English)

Swiss Database: COST-DB of the State Secretariat for Education and Research Hallwylstrasse 4 CH-3003 Berne, Switzerland Tel. [phone] Swiss Project-Number: C13.0038