The first rhodium‐catalyzed highly chemo‐, regio‐ and enantioselective hydroformylation of cyclopropyl‐functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. ...Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named (R,S)‐DTBM‐Yanphos, can convert a series of readily available cyclopropyl‐functionalized trisubstituted alkenes into high‐value chiral cyclopropyl‐functionalized aldehydes with high selectivities (81–98 % ee). Gram‐scale reactions (TON up to 1500) and follow‐up transformations to the corresponding alcohol, acid, esters and nitrile are also presented. Finally, a possible hydroformylation mechanism involving ring‐open‐hydroformylation pathways is proposed based on control and deuteroformylation reactions.
The first rhodium‐diphosphine‐catalyzed highly chemo‐, regio‐ and enantioselective hydroformylation of cyclopropyl‐functionalized trisubstituted alkenes to afford high‐value chiral cyclopropyl entities is reported. Insights into this transformation were established by control, deuteroformylation, and gram‐scale reactions (TON up to 1500). Versatile follow‐up transformations to the corresponding alcohol, acid, esters and nitrile were also demonstrated.
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Reported is an iridium catalyst for ortho‐selective C−H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen‐bond interactions. The ...BAIPy‐Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho‐C−H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C−H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion.
Organization is key: Direct ortho‐selective C−H borylation is extremely challenging. Reported here is the first example for direct ortho‐C−H borylation of valuable secondary aromatic amides, and it involves preorganization through hydrogen‐bond formation between the ligand and the amide group of the substrate. The new iridium catalyst is readily available and yields unprecedented regioselectivity for more than 26 substrates without the need for specific directing groups.
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The atom‐ and step‐efficient synthesis of chiral fused tricyclic lactams from readily available ketoesters using cheap ammonium salts as the nitrogen source is reported. This ruthenium‐catalyzed ...system operates through an efficient tandem dynamic kinetic asymmetric reductive amination (ARA)/lactamization and produces chiral fused tricyclic lactams in high yields with excellent diastereo‐ and enantioselectivity (up to >99 % ee, >20 : 1 dr and 98 % yield). The robust method was also applied to the concise synthesis of key intermediates in the synthesis of rivastigmine analogues and chiral N‐heterocyclic carbene catalysts.
An efficient and economical one‐pot approach to chiral fused tricyclic lactams from readily available ketoesters was developed by using cheap ammonium salts as the nitrogen source through ruthenium‐catalyzed tandem dynamic kinetic asymmetric reductive amination/lactamization. This protocol provides highly efficient access to drug intermediates and organocatalysts containing chiral polycyclic N‐heterocycles.
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In the context of a carbon neutral economy, catalytic CO2 hydrogenation to methanol is one crucial technology for CO2 mitigation providing solutions for manufacturing future fuels, chemicals, and ...materials. However, most of the presently known catalyst systems are used at temperatures over 220 °C, which limits the theoretical yield of methanol production due to the exothermic nature of this transformation. In this review, we summarize state-of-the-art catalysts, focusing on the rationales behind, for CO2 hydrogenation to methanol at temperatures lower than 170 °C. Both hydrogenation with homogeneous and heterogeneous catalysts is covered. Typically, additives (alcohols, amines or aminoalcohols) are used to transform CO2 into intermediates, which can further be reduced into methanol. In the first part, molecular catalysts are discussed, organized into: (1) monofunctional, (2) M/NH bifunctional, and (3) aromatization–dearomatization bifunctional molecular catalysts. In the second part, heterogeneous catalysts are elaborated, organized into: (1) metal/metal or metal/support, (2) active-site/N or active-site/OH bifunctional heterogeneous catalysts, and (3) cooperation of catalysts and additives in a tandem process via crucial intermediates. Although many insights have been gained in this transformation, in particular for molecular catalysts, the mechanisms in the presence of heterogeneous catalysts remain descriptive and insights unclear.
Propelled by the vision of carbon-neutral energy systems, heterogeneous hydrogenation of CO2 to formic acid/formate, a liquid hydrogen carrier, has been intensively studied as a promising approach to ...realize renewable and decarbonized energy supply. In the present review, the state-of-the-art of heterogeneous catalysts for this process is comprehensively summarized. First, a brief description of the challenges associated with thermodynamics is provided. Major advancements on constructing efficient heterogeneous catalysts then constitute the main body of this review, mainly involving nanostructured and single atom catalysts based on noble metals. Special attention is paid to the relevant structure–activity correlations and mechanistic insights, which provide strong bases for rational catalyst design. Key factors related to catalytic activity are highlighted including metal dispersion, electron density, basic functionalities, and concerted catalysis of metal and basic sites. A summary and outlook is presented in the end. We believe that this review will inspire more novel research from the catalysis community to advance the design of innovative catalytic materials towards the ultimate sustainable energy sector with a closed carbon loop.
The diagnosis of biliary atresia (BA) remains a clinical challenge because affected infants have signs, symptoms, and serum liver biochemistry that are also seen in those with other causes of ...neonatal cholestasis (non‐BA). However, an early diagnosis and prompt surgical treatment are required to improve clinical outcome. Recently, the relative abundance of serum matrix metalloproteinase‐7 (MMP‐7) was suggested to have discriminatory features for infants with BA. To test the hypothesis that elevated serum concentration of MMP‐7 is highly diagnostic for BA, we determined the normal serum concentration of MMP‐7 in healthy control infants, and then in 135 consecutive infants being evaluated for cholestasis. The median concentration for MMP‐7 was 2.86 ng/mL (interquartile range, IQR: 1.32‐5.32) in normal controls, 11.47 ng/mL (IQR: 8.54‐24.55) for non‐BA, and 121.1 ng/mL (IQR: 85.42‐224.4) for BA (P < 0.0001). The area under the curve of MMP‐7 for the diagnosis of BA was 0.9900 with a cutoff value of 52.85 ng/mL; the diagnostic sensitivity and specificity were 98.67% and 95.00%, respectively, with a negative predictive value of 98.28%. Conclusion: Serum MMP‐7 assay has high sensitivity and specificity to differentiate BA from other neonatal cholestasis, and may be a reliable biomarker for BA.
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A rolling bearing is an essential component of a rotating mechanical transmission system. Its performance and quality directly affects the life and reliability of machinery. Bearings’ performance and ...reliability need high requirements because of a more complex and poor working conditions of bearings. A bearing with high reliability reduces equipment operation accidents and equipment maintenance costs and achieves condition-based maintenance. First in this paper, the development of technology of the main individual physical condition monitoring and fault diagnosis of rolling bearings are introduced, then the fault diagnosis technology of multi-sensors information fusion is introduced, and finally, the advantages, disadvantages, and trends developed in the future of the detection main individual physics technology and multi-sensors information fusion technology are summarized. This paper is expected to provide the necessary basis for the follow-up study of the fault diagnosis of rolling bearings and a foundational knowledge for researchers about rolling bearings.
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DOBA, EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, IZUM, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, SIK, UILJ, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
In this work, the propagation of the surface ionization wave (SIW) in the nanosecond pulsed surface dielectric barrier discharge with different dielectric materials and pulse repetition rates is ...investigated. The current waveforms at different locations along the route of the SIW propagation are obtained, based on a specially designed ground strip array geometry. The temporal evolution and spatial distribution of the electric field during the SIW propagation are measured by using the electric field induced second harmonic generation method. The distribution of the residual surface potential after the discharge is mapped with a Kelvin electrostatic probe, which verifies both the existence of the residual electric field and its opposite direction to that during the SIW propagation. It is found that with the dielectric material on which the surface charges decay faster, there are the well-pronounced primary and secondary SIWs with a higher velocity on the voltage rising edge and both the peak current and the peak electric field are also higher, with a less spatial attenuation along the SIW propagation route. It is demonstrated that the residual surface charges with the same polarity as the high-voltage pulse suppress the development of the SIW.
A catalytic route is developed to synthesize bio‐renewable catechol from softwood‐derived lignin‐first monomers. This process concept consists of two steps: 1) O‐demethylation of 4‐n‐propylguaiacol ...(4‐PG) over acidic beta zeolites in hot pressurized liquid water delivering 4‐n‐propylcatechol (4‐PC); 2) gas‐phase C‐dealkylation of 4‐PC providing catechol and propylene over acidic ZSM‐5 zeolites in the presence of water. With large pore sized beta‐19 zeolite as catalyst, 4‐PC is formed with more than 93 % selectivity at nearly full conversion of 4‐PG. The acid‐catalyzed C‐dealkylation over ZSM‐5 zeolite with medium pore size gives a catechol yield of 75 %. Overall, around 70 % catechol yield is obtained from pure 4‐PG, or 56 % when starting from crude 4‐PG monomers obtained from softwood by lignin‐first RCF biorefinery. The selective cleavage of functional groups from biobased platform molecules through a green and sustainable process highlights the potential to shift feedstock from fossil oil to biomass, providing drop ins for the chemicals industry.
Pining for catechol: A catalytic route is developed to synthesize bio‐renewable catechol from pinewood‐derived lignin‐first monomers. The two‐step process consists of O‐demethylation of 4‐n‐propylguaiacol over acidic beta zeolites in hot pressurized liquid water, delivering 4‐n‐propylcatechol, and gas‐phase C‐dealkylation of 4‐propylcatechol providing catechol and propylene over acidic ZSM‐5 zeolites in the presence of water.
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