Article
Chemistry, Organic
Roxana Postolache, Juana M. Perez, Marta Castineira Reis, Luo Ge, Esther G. Sinnema, Syuzanna R. Harutyunyan
Summary: In this study, catalytic asymmetric hydrophosphination of α,β-unsaturated carbonyl derivatives using a chiral Mn(I) complex as a catalyst is reported. Various phosphine-containing chiral products can be obtained through H-P bond activation via hydrophosphination of different ketone, ester, and carboxamide-based Michael acceptors.
Article
Chemistry, Multidisciplinary
Josep Mas-Rosello, Christopher J. Cope, Eric Tan, Benjamin Pinson, Alan Robinson, Tomas Smejkal, Nicolai Cramer
Summary: Cyclometalated cyclopentadienyl iridium(III) complexes are efficient catalysts in the hydrogenation of oximes, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. The stable iridium C,N-chelation is crucial for the catalytic activity, and the hydrogenation system demonstrates high functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Dominique Matt, Jack Harrowfield
Summary: Tertiary phosphines and other P(III)-derivatives play a crucial role in homogeneous catalysis, especially compounds with cavity-shaped subunits. This review illustrates the utility of covalently-constructed phosphines that incorporate a cavity and highlights future directions in ligand design.
Article
Chemistry, Physical
Justin K. Kirkland, Jyothish Joy, Brooke L. Small, Julie A. Leseberg, Steven M. Bischof, Michael S. Webster-Gardiner, Daniel H. Ess
Summary: Through density functional theory and metadynamics calculations, our study on the aldehyde retro-hydroformylation pathway using cyclopentadienyl phosphine-type Ir(III) catalysts has revealed two surprising and unique aspects of catalysis: (1) The turnover of the catalytic cycle is determined by the rate of singlet-triplet spin state crossover; and (2) During catalysis, after C-H bond activation, a transient Ir-III-H intermediate undergoes intramolecular proton transfer to give a dearomatized η(4)-Cp-H diene ligand. These mechanistic insights provide a foundation for the design of novel retro-hydroformylation molecular catalysts.
Article
Chemistry, Organic
Huan Liu, Xufeng Lin, Da Yang
Summary: A series of novel Ir-complexes with different phosphine ligands were synthesized, and their effects on the catalysts performance were investigated. The results showed that Ir-complex modified by ionic bi-dentate phosphines with strong pi-accepting ability can effectively promote water gas shift reaction and hydroformylation of olefins, achieving high reaction yields.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jonathan Trouve, Paolo Zardi, Shaymaa Al-Shehimy, Thierry Roisnel, Rafael Gramage-Doria
Summary: Utilizing secondary interactions between substrates and catalysts is a promising approach to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are often discovered through trial-and-error screening, as small stereo-electronic modifications within the substrate and catalyst can lead to vastly different reactivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Miquel Navarro, Markus Holzapfel, Jesus Campos
Summary: A cavity-shaped gold(I) complex derived from a bulky tri-(ortho-biaryl)-phosphine ligand exhibits preferred selectivity towards terminal functionalities in the gold(I)-catalysed hydration of alkynes under mild heating, thanks to a well-defined pocket as the catalytic active site. This selectivity differs from other gold(I) complexes with bulky phosphine ligands, which show reduced selectivity or similar behavior towards both internal and terminal alkynes. We also explore the potential of gold(III) derivatives for the same catalytic process.
Review
Chemistry, Multidisciplinary
Hayato Fujimoto, Kosuke Yasu, Mamoru Tobisu
Summary: This report discusses recent studies on catalytic transformations involving a non-classical mode of molecular activation by tertiary phosphines and N-heterocyclic carbenes (NHCs). The results show that by designing specific catalytic protocols, synthetic transformations that are otherwise unattainable can be achieved, including intermolecular carbofluorination of alkynes and hydroalkenylation of enol ethers. The use of imidazolium-based NHCs was explored for nucleophilic aromatic substitution reactions as well as nucleophilic activation of styrene derivatives, generating non-stabilized vinyl anion equivalents.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Multidisciplinary
Jing Wang, Wenji Wang, Xiongyu Yang, Jingwen Liu, Haizhou Huang, Mingxin Chang
Summary: In this study, a practical homogeneous direct reductive amination (DRA) procedure using iridium catalysis was reported. The reaction conditions were mild and additive-free, allowing for the formation of structurally and functionally diverse amine products, including drugs and compounds from late-stage manipulation. DFT studies revealed that the reaction proceeds via an outer-sphere H-addition pathway with important roles played by pi-pi interactions and H-bonding.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Alexis Mifleur, Isabelle Suisse, Andre Mortreux, Mathieu Sauthier
Summary: The enantioselective hydroalkoxylation of butadiene with ethanol was achieved in the presence of nickel-based catalysts and chiral diphosphine ligands. Atropoisomeric chiral ligands like Segphos could yield Ee's up to 77%. Kinetics parameters were determined using a qualitative kinetic model, providing a better understanding of isomerization and racemization processes during the reaction.
Article
Chemistry, Physical
Jesus A. Avendano-Villarreal, Fabio G. Delolo, Artur V. Granato, Elena V. Gusevskaya, Eduardo N. dos Santos
Summary: A new and efficient method was developed to transform naturally occurring 1-propenylbenzenes into 2-arylpropylamines. This method involved a one-pot ethenolysis/hydroaminomethylation reaction and required careful selection of reaction conditions to achieve high yields. By adjusting the molar ratio of the catalysts, the interference between ethenolysis and hydroaminomethylation catalysts was avoided, resulting in the synthesis of nine 2-arylpropylamines with yields ranging from 75-93%.
Review
Chemistry, Applied
Pawan Kumar, Urvashi Sharma, Guddekoppa S. Ananthnag
Summary: This article provides a detailed overview of the synthesis, reactivity, structural features, and catalytic activities of acyl phosphines and bis(acyl) phosphines reported in the last three decades. Although acyl phosphines have been known historically, their literature is not exhaustive due to the vulnerability of P-C(O) bonds toward nucleophilic substitution reactions. However, there has been a renewed interest in the synthesis of acyl phosphines and di(acyl) phosphines recently, with the examples of phosphines possessing two acyl groups found more frequently in the literature. Transition-metal complexes of acyl phosphines and di(acyl) phosphines have been moderately explored, but their catalytic applications are limited.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tanuja Tewari, Rohit Kumar, Amol C. Chandanshive, Samir H. Chikkali
Summary: Metal-catalyzed hydroformylation and hydrogenation heavily rely on ligands, with phosphorus ligands playing a pivotal role. This account presents three distinct classes of phosphorus ligands, their synthesis, performance in reactions, and the latest developments in iron-catalyzed hydroformylation of alkenes. The use of phosphines enabled iron-catalyzed hydroformylation under mild conditions, demonstrating the central role of phosphorus ligands in industrially relevant transformations.
Review
Chemistry, Inorganic & Nuclear
Jeffery Wee Kiong Seah, Ronald Hong Xiang Teo, Pak-Hing Leung
Summary: Palladacycles with chiral chelating auxiliaries have been proven to be efficient catalysts for asymmetric hydrophosphination reactions, with the chiral auxiliaries remaining coordinated to the palladium centers during reactions and showing little susceptibility to catalyst poisoning. The unique stereoelectronic features and organometallic chemistry of palladacycle catalysts are essential for their synthetic operations.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Hao Deng, Marco Bengsch, Nico Tchorz, Constanze N. Neumann
Summary: This article introduces a novel method for fine-tuning phosphine ligands, which enables diversification of phosphine compounds by introducing different substituents into previously inaccessible positions. Compared to existing methods, this approach overcomes the limitations of phosphorus-directed reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Xinyi Ren, Lin Tang, Chaoren Shen, Huimin Li, Peng Wang, Kaiwu Dong
Summary: A palladium-catalyzed asymmetric hydroesterification-cyclization method was developed for efficient preparation of enantioenriched gamma-lactams, with good selectivities and a broad substrate scope. The correlation between multiple selectivities and N-substitutes of the amide linker in the substrate was demonstrated through crystallographic evidence and control experiments.
Article
Chemistry, Inorganic & Nuclear
Shu-Qing Yang, Yin-Qing Yao, Xiao-Chao Chen, Yong Lu, Xiao-Li Zhao, Ye Liu
Summary: The study investigates the mechanism of Pd-catalyzed amino dicarbonylation of aryl halides using different ligands, with the ionic diphosphine ligand L4 showing superior catalytic performance for achieving high conversion rates and selectivity.
Article
Nanoscience & Nanotechnology
Mengchen Shen, Guofeng Zhao, Qiang Nie, Chao Meng, Weidong Sun, Jiaqi Si, Ye Liu, Yong Lu
Summary: The development of a free-standing Ni-Al2O3 ensemble derived from NiAl-layered double hydroxides (NiAl-LDHs) grown onto a Ni-foam has proven to be effective in achieving a unique combination of high activity/selectivity and enhanced heat/mass transfer. The catalyst derived from un-calcined NiAl-LDH/Ni-foam exhibits a high turnover frequency and the capability to convert a high percentage of acetone into isopropanol with almost 100% selectivity.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Qiang Nie, Guofeng Zhao, Mengchen Shen, Ye Liu, Yong Lu
Summary: A bifunctional Ni-MoOx catalyst was developed for halide-free methanol carbonylation, with its performance strongly dependent on calcination/reduction temperature. The NiMo-350-600/SiO2 catalyst showed high methanol conversion and acetyls yield, with increased acetyls formation due to the presence of Ni0 and MoOx. MoO3 and NiMoO4 favored acetyls and DME formation, while MoNi4 and MoO2 enhanced DME production.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Multidisciplinary
Jiaqi Si, Guofeng Zhao, Weidong Sun, Jincun Liu, Cairu Guan, Yong Yang, Xue-Rong Shi, Yong Lu
Summary: This study reports a low-temperature active and selective MnOx-Na2WO4/SiO2 catalyst for the oxidative coupling of methane (OCM). The presence of Q(2) units in the SiO2 carrier is found to significantly lower the light-off temperature of the Mn3+ <-> Mn2+ redox cycle, enhancing the catalytic activity. Additionally, Na2WO4 promotes the reaction initiation and improves the selectivity towards C2-3 products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Kai-Chun Zhao, Lei Liu, Xiao-Chao Chen, Yin-Qing Yao, Lin Guo, Yong Lu, Xiao-Li Zhao, Ye Liu
Summary: A series of diphosphine ligands containing bis-phosphino fragments and bis-amido groups have been synthesized and their effects on the catalytic activity of Pd complexes have been investigated. Among these ligands, L5 exhibits a synergistic catalytic effect, leading to higher activity and yields in the alkoxycarbonylation reaction of alkynes with methanol.
Article
Chemistry, Physical
Guofeng Zhao, Jiayong Ni, Jiaqi Si, Weidong Sun, Yong Lu
Summary: This article reviews the recent studies on the low-temperature light-off Mn2+<-> Mn3+ redox cycle over MnOx-Na2WO4-based catalysts and highlights its positive effect on reducing the ignition temperature of OCM. In addition, three perspectives for the industrialization of OCM based on this concept are discussed.
Article
Chemistry, Physical
Xiao-Chao Chen, Tian Lan, Kai-Chun Zhao, Lin Guo, Yong Lu, Ye Liu
Summary: This study developed a new P,O-hybrid ligand and successfully synthesized a stable Rh-complex Z, which exhibited excellent catalytic activity to accelerate each individual step in the tandem hydroaminomethylation (HAM) reaction and inhibit the side-reaction of olefin-hydrogenation.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Qiang Nie, Jiaqi Si, Chao Meng, Tian Lan, Weidong Sun, Guofeng Zhao, Ye Liu, Yong Lu
Summary: The Cu/Sn-beta system enables efficient synthesis of methyl acetate with high selectivity and low methanol conversion. The catalyst facilitates the formation of bridged-adsorbed CH2O* through electron transfer and Cu(0) dehydrogenation, and further transforms it into formaldehyde through a C-C coupling reaction. Finally, formaldehyde condenses with adsorbed CH3O* on the Cu-0 site to form methyl acetate.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Xiao-Chao Chen, Tian Lan, Jian Zhu, Sibin Ying, Guang-Hui Shi, Kai -Chun Zhao, Lin Guo, Yong Lu, Ye Liu
Summary: In this study, the tripodal phosphine L1 was used to control the activity, regioselectivity, and stability of the Pd-catalyst in the synthesis of linear amides. The unique characteristics of L1, such as its steric bulkiness, switching-coordination mode, and robustness against moisture and oxygen, contributed to the high activity, good regioselectivity, and excellent stability of the Pd-catalyst.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Jiaqi Si, Guofeng Zhao, Tian Lan, Jiayong Ni, Weidong Sun, Ye Liu, Yong Lu
Summary: The study reveals that Na2WO4 plays a crucial role in reducing the trigger temperature and selectively activating the Mn7SiO12 <-> MnSiO3 redox reaction in the OCM process. It also shows that oxygen exchange between O2 and Na2WO4 only occurs in case of re-oxidizing MnWO4 formed during the reaction at high temperatures.
Article
Chemistry, Organic
Yi-Ying Zhuang, Xiao-Chao Chen, Kai-Chun Zhao, Guo-Sheng Zhang, Yu-Fen Xie, Yong Lu, Ye Liu
Summary: This work was financially supported by the National Natural Science Foundation of China (Nos. 22172052 and 21972045), and the Research Funds of Happiness Flower ECNU (2022ST2203).
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Guofeng Zhao, Jacob A. Moulijn, Frederik Kapteijn, Frits M. Dautzenberg, Bin Xu, Yong Lu
Summary: Heterogeneous catalysis is crucial in current chemical and energy production. The use of fiber/foam-substrates with non-dipcoating methods shows great potential in addressing the limitations of traditional packed-bed reactors and improving reaction efficiency.
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING
(2023)
Article
Chemistry, Physical
Guang-Hui Shi, Xiao-Chao Chen, Tian-hong Jing, Yi-Ying Zhuang, Yong Lu, Ye Liu
Summary: The first-step hydroformylation of allyl acetate was studied for the synthesis of 1,4-butanediol via a two-step hydroformylation-hydrogenation sequence. The Xantphos-modified Rh(acac)(CO)2 catalytic system showed high efficiency, with a yield of 80% for the target product of 4-acetoxybutanal. The catalytic system exhibited excellent regioselectivity and recyclability, making it suitable for large-scale applications. Control experiments were conducted to understand the reaction pathways for the formation of the target product and related side-products.
MOLECULAR CATALYSIS
(2023)
Article
Energy & Fuels
Shuang Xue, Tian Lan, Guofeng Zhao, Qiang Nie, Chao Meng, Xinyi Xu, Yong Lu
Summary: In this study, a highly active and selective NiCx/Ni-foam catalyst is reported, which is obtained by the endogenous growth of NiC2O4 onto a Ni-foam and subsequent H2-reduction treatment. The preferred catalyst with high content of NiCx is capable of converting 63.6% or 94.3% CO at 350 degrees C or 400 degrees C with trace or < 0.8% CH4 formation for a feed gas with H2O/CO/Ar molar ratio of 4/1/9, and is stable for at least 110 h. It is experimentally and theoretically revealed that the Ni3C facilitates the dissociative activation of H2O and favors CO to form carboxylate species (favorable for CO2 formation) rather than active Ni(CO)n intermediates for CH4 formation thereby enabling the catalyst with high WGSR activity and selectivity.
