Phosphorus-Doped Carbon-Supported Rh Nanoparticles for the Hydroformylation of Styrene with High Regioselectivity

Zhang, Xingcong; Zhang, Hao; Guo, Guanghui; Sun, Qingdi; He, Xiaohui; Ji, Hongbing

doi:10.1021/acs.iecr.2c04328

Cited by 4 publications

(2 citation statements)

References 26 publications

(41 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Owing to the flexibility in the functional group chemistry on styrene monomers, and method involving copolymers, polystyrene with exceptional chemical and physical properties can be designed for specific applications, for instance, disposable packing in consumer products or heat-resistant polymer for industrial applications. , One such example of heat-resistant styrene is the α-alkyl styrene which can also be functionalized and modified for further derivatization. − Unfortunately, α-alkyl styrenes are difficult to produce due to a relative shortage of efficient synthetic methodologies. In most cases, aryl ketones are converted to terminal alkenes using Wittig reagents, , but this method is limited only to synthesis of α-alkyl styrenes with simple alkyl groups. − Some methods of α-alkyl styrene synthesis involving carbon-supported rhodium nanoparticle-assisted catalysis provide avenues for regioselective addition of branched or linear aldehydes . However, other existing methods require pre-existing α-methyl or other reactive groups in place at the α position.…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Insight into 1,2-Shift Rearrangement in Bromination of Allylaryls

Hardy,

Isbel,

Bugarin

et al. 2023

ACS Omega

View full text Add to dashboard Cite

In this work, we have provided mechanistic insight into the addition of bromine to an allylic double bond of allylaryl derivatives using experimental and DFT-based electronic structure methods. The experimental yields indicate the influence of the functional group on the aryl ring on the ratio of 1,2-dibromo and 1,3-dibromo adducts formed in the reaction. The optimized geometry and the electron density maps of the allylaryls and their cationic intermediates from DFT simulations revealed that electron-rich aryl rings promoted formation of cationic spiro[2.5] intermediate II, whereas electron-poor aryl rings resulted in formation of bromonium intermediate I. It was observed that electron-rich allylaryls promoted the 1,2-shift of the aryl ring that resulted in bond formation between the carbon atom (C1) on the aryl ring and the central carbon atom (C3) in the allylic double bond and formed spiro[2.5] intermediate II, a trend which was confirmed by harmonic oscillator model of aromaticity index. Also, Wiberg bond order analysis is in good agreement with the experimental work. Thermochemical analysis indicates that smaller C1···C3 distance resulted in favorable values for the difference in free energy change (ΔΔG). The favorable ΔΔG values are a result of higher electron density on the aryl ring, making it more nucleophilic toward C3 carbon and promoting 1,2-shift that led to formation of the spiro[2.5] intermediate. Thus, the underlying mechanism indicates that the electron-rich allylaryls promote the formation of 1,3-dibromo compounds through formation and stabilization of the spiro[2.5] intermediate II.

show abstract

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Insight into 1,2-Shift Rearrangement in Bromination of Allylaryls

Hardy,

Isbel,

Bugarin

et al. 2023

ACS Omega

View full text Add to dashboard Cite

show abstract

“…Recently, mechanochemical methods (ball milling) have attracted wide attention due to their advantages of simple operation and trace or even solvent-free. The ball milling method has been successfully adopted for the synthesis of various materials and catalysts, which display great advantages in the preparation of SACs without scaling effect in large-scale preparation of SACs . For example, He and co-workers successfully achieved the kilogram preparation of Pd 1 /ZnO by the ball milling for the phenylacetylene semihydrogenation .…”

Section: Introductionmentioning

confidence: 99%

Selective Hydrogenation of Aromatic Ketone to Aromatic Alcohol over Pd Single-Atom Catalysts

Guo,

Zhang,

Zhang

et al. 2023

Ind. Eng. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Aromatic alcohols prepared by hydrogenation of aromatic ketones are an important kind of intermediate that are widely used in the production of fine chemicals. Single-atom catalysts (SACs) are considered ideal alternatives to conventional heterogeneous catalysts due to their unique geometrical structure. Herein, we report the palladium SACs supported by titanium oxide (Pd 1 /TiO 2 SACs) successfully synthesized via a simple and efficient ball milling process. In the hydrogenation of acetophenone to 1-phenylethanol, Pd 1 /TiO 2 SACs exhibit higher conversion and selectivity than Pd n /TiO 2 nanoparticle catalysts. Also, Pd 1 /TiO 2 SACs exhibit excellent hydrogenation for a range of compounds containing C�O bonds.

show abstract

Catalytic hydroformylation of alkenes to branched aldehydes promoted by water on Rh nanoclusters-anchored porous triphenylphosphine frameworks

Wang,

Zeng,

Fang

et al. 2024

Chemical Engineering Journal

View full text Add to dashboard Cite

Phosphorus-Doped Carbon-Supported Rh Nanoparticles for the Hydroformylation of Styrene with High Regioselectivity

Cited by 4 publications

References 26 publications

Quantum Chemical Insight into 1,2-Shift Rearrangement in Bromination of Allylaryls

Quantum Chemical Insight into 1,2-Shift Rearrangement in Bromination of Allylaryls

Selective Hydrogenation of Aromatic Ketone to Aromatic Alcohol over Pd Single-Atom Catalysts

Catalytic hydroformylation of alkenes to branched aldehydes promoted by water on Rh nanoclusters-anchored porous triphenylphosphine frameworks

Contact Info

Product

Resources

About