title: Readily Accessible Bulky Iron Catalysts exhibiting Site Selectivity in the Oxidation of Steroidal Substrates.
abstract: Bulky iron complexes are described that catalyze the site-selective oxidation of alkyl C-H bonds with hydrogen peroxide under mild conditions. Steric bulk at the iron center is introduced by appending trialkylsilyl groups at the meta-position of the pyridines in tetradentate aminopyridine ligands, and this effect translates into high product yields, an enhanced preferential oxidation of secondary over tertiary C-H bonds, and the ability to perform site-selective oxidation of methylenic sites in terpenoid and steroidal substrates. Unprecedented site selective oxidation at C6 and C12 methylenic sites in steroidal substrates is shown to be governed by the chirality of the catalysts.
authors.affiliation: Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: David
authors.initials: D
authors.lastname: Font
authors.affiliation: Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Mercè
authors.initials: M
authors.lastname: Canta
authors.affiliation: Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Michela
authors.initials: M
authors.lastname: Milan
authors.affiliation: Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Olaf
authors.initials: O
authors.lastname: Cussó
authors.affiliation: Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain.
authors.forename: Xavi
authors.initials: X
authors.lastname: Ribas
authors.affiliation: Organic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584, CG Utrecht, The Netherlands. r.j.m.kleingebbink@uu.nl.
authors.forename: Robertus J M
authors.initials: RJ
authors.lastname: Klein Gebbink
authors.affiliation: Institut de Química Computacional I Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071, Girona, Catalonia, Spain. miquel.costas@udg.edu.
authors.forename: Miquel
authors.identifier: 0000-0001-6326-8299
authors.initials: M
authors.lastname: Costas
mesh_terms: D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013256:Steroids / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D013256:Steroids; D002244:Carbon; D006859:Hydrogen; D006861:Hydrogen Peroxide; D007501:Iron
keywords: C−H activation; asymmetric catalysis; bioinspired catalysis; iron; selective oxidation