74483-92-4Relevant articles and documents
High-Spin and Low-Spin State Perferryl Intermediates: Reactivity-Selectivity Correlation in Fe(PDP) Catalyzed Oxidation of (+)-Sclareolide
Zima, Alexandra M.,Babushkin, Dmitrii E.,Lyakin, Oleg Y.,Bryliakov, Konstantin P.,Talsi, Evgenii P.
, (2021/12/03)
Five iron complexes of the Fe(PDP) family, giving rise to the low-spin (S=1/2) and high-spin (S=3/2) perferryl oxygen-transferring intermediates, have been screened in the C?H oxidation of the bulky steroidal substrate (3aR)-(+)-sclareolide with H2/
Catalyst-controlled aliphatic C—H oxidations
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Page/Page column 37; 61; 63, (2018/04/20)
The invention provides simple small molecule, non-heme iron catalyst systems with broad substrate scope that can predictably enhance or overturn a substrate's inherent reactivity preference for sp3-hybridized C—H bond oxidation. The invention also provides methods for selective aliphatic C—H bond oxidation. Furthermore, a structure-based catalyst reactivity model is disclosed that quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst. The catalyst systems can be used in combination with oxidants such as hydrogen peroxide to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates.
Making Fe(BPBP)-catalyzed C-H and CC oxidations more affordable
Yazerski, Vital A.,Spannring, Peter,Gatineau, David,Woerde, Charlotte H.M.,Wieclawska, Sara M.,Lutz, Martin,Kleijn, Henk,Klein Gebbink, Robertus J.M.
supporting information, p. 2062 - 2070 (2014/03/21)
The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α- [Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf) 2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C-H and C=C bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp3 C-H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude dl/meso-2,2′-bipyrrolidine. Next to its use in C-H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.
