529-33-9Relevant articles and documents
Synergistic effects of encapsulated phthalocyanine complexes in MIL-101 for the selective aerobic oxidation of tetralin
Kockrick, Emanuel,Lescouet, Tristan,Kudrik, Evgeny V.,Sorokin, Alexander B.,Farrusseng, David
, p. 1562 - 1564 (2011)
Metal phthalocyanine complexes encapsulated in MIL-101, and used as "ship-in-a-bottle" catalysts, show outstanding TONs in the aerobic oxidation of tetralin.
Gross et al.
, p. 55,56, 57, 58, 59 (1977)
Coordination frameworks assembled from CuII ions and H2-1,3-bdpb ligands: X-ray and magneto structural investigations, and catalytic activity in the aerobic oxidation of tetralin
Grzywa, MacIej,Gessner, Christof,Bredenk?tter, Bj?rn,Denysenko, Dmytro,Van Leusen, Jan,K?gerler, Paul,Klemm, Elias,Volkmer, Dirk
, p. 16846 - 16856 (2014)
The syntheses and crystal structures of H2-1,3-bdpb·MeOH, [CuII2(1,3-bdpb)(OCH3)2] (CFA-5) and [CuICl(H2-1,3-bdpb)] (H2-1,3-bdpb = 1,3-bis(3,5-dimethyl-1H-pyrazol-4-yl)benzene) are described. The copper(ii) containing metal-organic framework (termed Coordination Framework Augsburg University-5, CFA-5) crystallizes in the trigonal crystal system, within the space group R3 (no. 148) and the unit cell parameters are as follows: a = 26.839(3), c = 15.8317(16) ?, V = 9876.2(19) ?3. CFA-5 features a two-fold interpenetrated 3-D microporous framework structure of cross-linked wheel-shaped {CuII(pz)(OMe)}12 fundamental building units, each containing twelve copper(ii) ions, μ2-bridging MeO- groups and pyrazolate (pz-) ligands. Replacing copper(ii) acetate by copper(ii) chloride in the synthesis leads to compound [CuICl(H2-1,3-bdpb)], which crystallizes in the orthorhombic crystal system, within the space group Pnma (no. 62) and the unit cell parameters are as follows: a = 6.1784(8), b = 6.1784(8), c = 6.1784(8) ?, V = 1583.8(4) ?3. In contrast to the former compound, CuCl(H2-1,3-bdpb) is a non-porous compound consisting of CuI-Cl zigzag chains expanding in the direction [100] and H2-1,3-bdpb ligands. CFA-5 is characterized by elemental and thermogravimetric analyses, variable temperature powder X-ray diffraction and IR-spectroscopy; and its porosity and magnetic properties are described in detail. CFA-5 shows a promising catalytic activity in the heterogeneously catalyzed aerobic oxidation of tetralin, which is compared with other catalytically active metal-organic frameworks.
Meso-Substitution Activates Oxoiron(IV) Porphyrin π-Cation Radical Complex More Than Pyrrole-β-Substitution for Atom Transfer Reaction
Fukui, Nami,Ueno, Kanako,Hada, Masahiko,Fujii, Hiroshi
, p. 3207 - 3217 (2021)
There have been two known categories of porphyrins: a meso-substituted porphyrin like meso-tetramesitylporphyrin (TMP) and a pyrrole-β-substituted porphyrin like native porphyrins and 2,7,12,17-tetramethyl-3,8,13,18-tetramesitylporphyrin (TMTMP). To reveal the chemical and biological function of native hemes, we compare the reactivity of the oxoiron(IV) porphyrin π-cation radical complex (Compound I) of TMP (TMP-I) with that of TMTMP (TMTMP-I) for epoxidation, hydrogen abstraction, hydroxylation, sulfoxidation, and demethylation reactions. Kinetic analysis of these reactions indicated that TMP-I is much more reactive than TMTMP-I when the substrate is not sterically bulky. However, as the substrate is sterically bulkier, the difference of the reactivity between TMP-I and TMTMP-I becomes smaller, and the reactivity of TMP-I is comparable to that of TMTMP-I for a sterically hindered substrate. Since the redox potential of TMP-I is almost the same as that of TMTMP-I, we conclude that TMP-I is intrinsically more reactive than TMTMP-I for these atom transfer reactions, but the steric effect of TMP-I is stronger than that of TMTMP-I. This is contrary to the previous result for the single electron transfer reaction: TMTMP-I is faster than TMP-I. DFT calculations indicate that the orbital energies of the Fe=O moiety for TMTMP-I are higher than those for TMP-I. The difference in steric effect between TMP-I and TMTMP-I is explained by the distance from the mesityl group to the oxo ligand of Compound I. Significance of the pyrrole-β-substituted structure of the hemes in native enzymes is also discussed on the basis of this study.
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Wolf,P.F. et al.
, p. 1875 - 1882 (1975)
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Selective Decomposition of Tetralin Hydroperoxide Catalysed by Quaternary Ammonium Salts
Napadensky, Eduardo,Sasson, Yoel
, p. 65 - 66 (1991)
Tetralin hydroperoxide decomposes to 1-tetralone via a hydrogen bond complex with quaternary ammonium salt catalysts.
Enhancing the Catalytic Performance of a CYP116B Monooxygenase by Transdomain Combination Mutagenesis
Li, Ren-Jie,Xu, Jian-He,Chen, Qi,Zhao, Jing,Li, Ai-Tao,Yu, Hui-Lei
, p. 2962 - 2968 (2018)
The cytochrome P450 monooxygenase discovered in Labrenzia aggregata (P450LaMO) is a self-sufficient redox system with versatile oxygenation functions. However, its catalytic performance is severely hindered by a low reaction rate, poor electron coupling efficiency (CE) and fragile thermostability. Herein, a simple transdomain combination mutation strategy was proposed for engineering this multi-domain P450 enzyme with redox partners fused to the heme domain. After focused mutagenesis on the heme domain, a triple mutant H3 (N119C/V264A/V437G) was hit, that improved the turnover frequency (TOF) and CE of P450LaMO by about 7.8-fold and 3.0-fold, respectively. A redox domain-based mutant with higher cytochrome c reduction activity, MR1 (M612L/K774Y), mediated more efficient electron transfer, elevated the TOF by 4.9-fold, and the coupling efficiency by 4.2-fold. The beneficial effect was further enhanced by combining the mutation sites from different domains, resulting in a combinatorial mutant (N119C/V264A/V437G/M612L/N694D) with a 9.1-fold increase in coupling efficiency, 10-fold in TOF, as well as +3.8 °C in thermostability (T5010). Meanwhile, for series of tetrahydronaphthalene derivatives, this combinator showed higher hydroxylation activity. This work suggested that employing this combinatorial strategy targeting on both the redox and heme domains is efficient to improve holoenzyme activity, CE and stability of a CYP116B subfamily member from the low starting point.
Biphasic autoxidation of tetralin catalyzed by surface-active transition metal complexes
Ahn, Wha Seung,Zhong, Yaping,Abrams, Cameron F.,Lim,Brown, Phillip A.
, p. 596 - 602 (1997)
Biphasic autoxidation of tetralin has been carried out using surface-active tetramethylethylenediamine complexes of manganese, chromium, and nickel as catalysts, tetralin as the substrate and organic phase, and dodecyl sodium sulfate as emulsifier. Advantages of the biphasic reaction over the homogeneous and heterogeneous counterparts include avoidance of the use of a troublesome solvent, ease of catalyst recovery and substrate recycle, and attainment of high reactivity, selectivity, and reproducibility under mild reaction conditions (T a?? 60 ?°C, P a?? 1 atm). The main reaction products are ?±-tetralone and ?±-tetralol. The selectivity for the former decreases from 95% with the chromium complex to 90% with the nickel complex and 60% with the manganese complex, and the activity varies in a reverse order. The biphasic reaction stops at a bulk tetralin conversion of 35% due to the buildup of inhibitive, higher oxidation products. Similar product inhibition has been reported in one-liquid-phase systems. The biphasic scheme, however, permits a more convenient recovery and recycle of the catalyst and unreacted substrate. The reaction order with respect to oxygen decreases from 1.0 to 0 above an oxygen pressure of 0.15 atm. The reaction order with respect to catalyst decreases from 2.0 or 1.4 to 1.0 and then 0 with increasing metal concentration. Manganese switches role from catalyst to inhibitor above a threshold metal concentration, as indicated by a lengthening of the induction period of the reaction. A generalized reaction mechanism is proposed which yields model results in good agreement with the experimental findings.
Synthesis of a sulfonato-salen-nickel(ii) complex immobilized in LDH for tetralin oxidation
Bhattacharjee, Samiran,Jeong, Kwang-Eun,Jeong, Soon-Yong,Ahn, Wha-Seung
, p. 156 - 162 (2010)
A novel sulfonato-salen-nickel(ii) complex has been immobilized on a Zn(ii)-Al(iii) layered double hydroxide (LDH) host. XRD, FT-IR, TGA and UV-vis spectroscopy, as well as chemical analysis, confirmed the successful incorporation of the nickel-salen complex within the LDH structure. BET surface area measurements, SEM and TEM were also used to characterize the heterogenized catalyst. The sulfonato-salen-nickel(ii) complex-immobilized material, LDH-[nickel-salen], was found to be effective in the oxidation of tetralin, where a combination of trimethylacetaldehyde and dioxygen at atmospheric pressure was employed as the oxidant. At 72.3% conversion, tetralin was converted to 1-tetralone with 72.2% selectivity at 70 °C after 7 h. Tetralin oxidation using tert-butyl hydroperoxide afforded a lower conversion and selectivity of 1-tetralone than with trimethylacetaldehyde and dioxygen as the oxidant. The effect of various reaction parameters on catalytic performance was also investigated. A hot filtration experiment coupled with a blank test revealed that oxidation proceeded mostly on nickel-salen sites in LDH-[nickel-salen]. A reaction mechanism is proposed based on the experimental results.
Platinum thiolate complexes supported by PBP and POCOP pincer ligands as efficient catalysts for the hydrosilylation of carbonyl compounds
Chang, Jiarui,Chen, Xuenian,Xue, Man-Man,Zhang, Jie
supporting information, p. 2304 - 2312 (2022/02/21)
Diphosphino-boryl-based PBP pincer platinum thiolate complexes, [Pt(SR){B(NCH2PtBu2)2-1,2-C6H4}] (R = H, 1a; Ph, 1b), and benzene-based bisphosphinite POCOP pincer platinum thiolate complexes, [Pt(SR)(tBu2PO)2-1,3-C6H3] (R = H, 2a; Ph, 2b), were prepared
Fe-Catalyzed Anaerobic Mukaiyama-Type Hydration of Alkenes using Nitroarenes
Bhunia, Anup,Bergander, Klaus,Daniliuc, Constantin Gabriel,Studer, Armido
supporting information, p. 8313 - 8320 (2021/03/08)
Hydration of alkenes using first row transition metals (Fe, Co, Mn) under oxygen atmosphere (Mukaiyama-type hydration) is highly practical for alkene functionalization in complex synthesis. Different hydration protocols have been developed, however, control of the stereoselectivity remains a challenge. Herein, highly diastereoselective Fe-catalyzed anaerobic Markovnikov-selective hydration of alkenes using nitroarenes as oxygenation reagents is reported. The nitro moiety is not well explored in radical chemistry and nitroarenes are known to suppress free radical processes. Our findings show the potential of cheap nitroarenes as oxygen donors in radical transformations. Secondary and tertiary alcohols were prepared with excellent Markovnikov-selectivity. The method features large functional group tolerance and is also applicable for late-stage chemical functionalization. The anaerobic protocol outperforms existing hydration methodology in terms of reaction efficiency and selectivity.
