959395-07-4Relevant articles and documents
H2O2 activation with biomimetic non-haem iron complexes and AcOH: Connecting the g = 2.7 EPR signal with a visible chromophore
Makhlynets, Olga V.,Oloo, Williamson N.,Moroz, Yurii S.,Belaya, Irina G.,Palluccio, Taryn D.,Filatov, Alexander S,Mueller, Peter,Cranswick, Matthew A.,Que, Lawrence,Rybak-Akimova, Elena V.
, p. 645 - 648 (2014)
Mechanistic studies of H2O2 activation by complexes related to [(BPMEN)FeII(CH3CN)2]2+ with electron-rich pyridines revealed that a new intermediate formed in the presence of acetic acid with a 465 nm visible band can be associated with an unusual g = 2.7 EPR signal. We postulate that this chromophore is an acylperoxoiron(iii) intermediate.
Synthesis of water-soluble Ni(II) complexes and their role in photo-induced electron transfer with MPA-CdTe quantum dots
Botcha, Niharika Krishna,Gutha, Rithvik R.,Sadeghi, Seyed M.,Mukherjee, Anusree
, p. 143 - 153 (2019/09/10)
Abstract: Photocatalytic water splitting using solar energy for hydrogen production offers a promising alternative form of storable and clean energy for the future. To design an artificial photosynthesis system that is cost-effective and scalable, earth a
Effects of denticity and ligand rigidity on reactivity of copper complexes with cumyl hydroperoxide
Pella, Bruce J.,Niklas, Jens,Poluektov, Oleg G.,Mukherjee, Anusree
, p. 71 - 78 (2018/08/21)
Cu(II) complexes bearing N2/Py2 tetradentate ligands consisting of two pyridyl arms and a flexible ethyldiamine backbone, [(BPMEN)Cu(ClO4)2] (1), with rigid cyclohexyl backbone [(BPMCN)Cu(ClO4)2] (2), and substituted with bispyrrolidyl [(PDP)Cu(ClO4)2] (3), and Cu(II) complex bearing N2/Py3 pentadentate ligand, [(TPMEN)Cu(ClO4)2] (4), were synthesized and structurally characterized. Reactivity of 1–4 with cumyl hydroperoxide was investigated to study the effects of ligand rigidity and denticity on the mechanism of O–O bond cleavage. Results presented herein illustrate that 1–3 favors homolysis, however 4 showed little to almost no impact on O–O bond cleavage.
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.
Asymmetric epoxidation with H2O2 by manipulating the electronic properties of non-heme iron catalysts
Cusso, Olaf,Garcia-Bosch, Isaac,Ribas, Xavi,Lloret-Fillol, Julio,Costas, Miquel
supporting information, p. 14871 - 14878 (2013/10/22)
A non-heme iron complex that catalyzes highly enantioselective epoxidation of olefins with H2O2 is described. Improvement of enantiomeric excesses is attained by the use of catalytic amounts of carboxylic acid additives. Electronic effects imposed by the ligand on the iron center are shown to synergistically cooperate with catalytic amounts of carboxylic acids in promoting efficient O-O cleavage and creating highly chemo-and enantioselective epoxidizing species which provide a broad range of epoxides in synthetically valuable yields and short reaction times.
Selective Aliphatic C-H Oxidation
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Page/Page column 11, (2011/02/18)
A composition including a complex of a metal, a tetradentate ligand, at least one ancillary ligand, and a counterion may be used for selective sp3 C—H bond oxidation. The tetradentate ligand may include a N-heterocyclic-N,N′-bis(pyridyl)-ethane-1,2-diamine group or a N,N′-bis(heterocyclic)-N,N′-bis(pyridyl)-ethane-1,2-diamine group. The composition can be used in combination with H2O2 to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates. The site of oxidation can be predicted, based on the electronic and/or steric environment of the C—H bond. In addition, the oxidation reaction does not require the presence of directing groups in the substrate.
Short asymmetric synthesis of (S,S)-PDP using l-prolinol derivative as economic starting material
Song, Xiao-Nan,Yao, Zhu-Jun
experimental part, p. 2589 - 2593 (2010/05/01)
(S,S)-PDP (5d) and its backbone (2S,2′S)-bipyrrolidine (1) have been extensively applied as the scaffold of various chiral ligands in catalytic asymmetric syntheses. In this study, new short asymmetric syntheses of these two important C2-symmetrical nitrogen heterocycles have been accomplished employing economically available l-prolinol derivative 10 as the starting material. Excellent diastereoselectivity was achieved of the key Grignard addition to imine intermediate utilizing (S)-N-tert-butanesulfinamide as the chiral auxiliary.
Selective Aliphatic C-H Oxidation
-
, (2009/09/08)
A composition including a complex of a metal, a tetradentate ligand, at least one ancillary ligand, and a counterion may be used for selective sp3 C—H bond oxidation. The tetradentate ligand may include a N-heterocyclic-N,N′-bis(pyridyl)-ethane-1,2-diamine group or a N,N′-bis(heterocyclic)-N,N′-bis(pyridyl)-ethane-1,2-diamine group. The composition can be used in combination with H2O2 to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates. The site of oxidation can be predicted, based on the electronic and/or steric environment of the C—H bond. In addition, the oxidation reaction does not require the presence of directing groups in the substrate.