Article
Chemistry, Multidisciplinary
Ierasia Triandafillidi, Maroula G. Kokotou, Dominik Lotter, Christof Sparr, Christoforos G. Kokotos
Summary: The organocatalytic epoxidation of unactivated alkenes using aqueous hydrogen peroxide provides essential products and intermediates in a sustainable manner. A specific atropisomeric two-axis aldehyde was identified for high-yielding epoxidations of cyclic and acyclic alkenes, resulting in high catalytic efficiencies due to the proximity of the aldehyde and backbone residues. Mechanistic studies suggest a non-radical alkene oxidation by an aldehyde-derived dioxirane intermediate generated from hydrogen peroxide through the Payne and Criegee intermediates.
Article
Chemistry, Organic
Rodney A. Fernandes, Sandhya S. Yadav, Praveen Kumar
Summary: This paper presents an efficient palladium-catalyzed anti-Markovnikov oxidative acetalization of activated terminal olefins with iron(iii) sulfate as the reoxidant, under mild reaction conditions. The methodology exhibits high regioselectivity towards anti-Markovnikov products and compatibility with a wide range of functional groups. Iron(iii) sulfate is the sole reoxidant used, providing various anti-Markovnikov acetals, including orthogonally functionalized 1,3- and 1,4-dioxygenated compounds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Purushothaman Rajeshwaran, Jonathan Trouve, Khalil Youssef, Rafael Gramage-Doria
Summary: The Wacker reaction is a significant industrial transformation that oxidizes olefins to ketones. However, it typically requires expensive palladium catalysts, which has led to the development of Wacker-type processes that avoid their use, allowing for more sustainable procedures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Shu-Hui Lei, Ya Zhong, Xian-Peng Cai, Qing Huang, Jian-Ping Qu, Yan-Biao Kang
Summary: A tandem isomerization-anti-Markovnikov oxidation method has been developed using bis(benzonitrile)palladium chloride catalyst and O-2 as the sole oxidant, regiospecifically yielding beta-amino aldehydes. tert-Butyl nitrite serves as a simple and only redox cocatalyst, with (BuOH)-Bu-t as a crucial solvent for achieving excellent yield and specificity toward anti-Markovnikov aldehyde products.
Article
Chemistry, Organic
Shu-Hui Lei, Ya Zhong, Xian-Peng Cai, Qing Huang, Jian-Ping Qu, Yan-Biao Kang
Summary: A simple and practical method for the preparation of beta-O substituted aldehydes directly from linear allylic esters has been developed. By using a specific catalyst and oxidant, the reaction proceeds smoothly to give the desired products, showing broad substrate scope and excellent regioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Mayu Miyazaki, Yasuyuki Ura
Summary: This study demonstrates the efficient oxidation of aliphatic terminal alkenes using a Pd/Fe catalyst system under mild reaction conditions. The use of a specific mixed solvent and gradual addition of alkenes improves the product yields. Fe(III) citrate is found to be the most efficient cocatalyst, but other iron complexes also show similar effects. Furthermore, this method is applicable to aliphatic internal alkenes that are generally difficult to oxidize, and gram-scale synthesis and reuse of the Pd catalysts are demonstrated.
Article
Chemistry, Organic
Rina Tanaka, Saki Komori, Yuhei Shimizu, Yasutaka Kataoka, Yasuyuki Ura
Summary: The steric hindrance of 1,1-disubstituted alkenes makes their Wacker-type oxidation challenging. In this study, we successfully demonstrated the stereoselective synthesis of 2-hydroxytetrahydrofurans by utilizing a PdCl2(MeCN)(2)/NO/BQ catalyst system under 1 atm O-2 in H2O or H2O/DMF.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qi Zhao, Lirong Zheng, Yixuan Gao, Jingjing Li, Juanjuan Wei, Min Zhang, Jianghui Sun, Jin Ouyang, Na Na
Summary: An aptamer-functionalized Pd@MoO3-x nano-hydrangea (A-Pd@MoO3-x NH) with dual active centers has been developed to overcome the adverse effects of the tumor microenvironment (TME) and achieve high-efficiency cancer therapy. This nanozyme can address tumor hypoxia and high endogenous glutathione (GSH) through cascade enzymatic reactions, catalyzing the degradation of GSH and mitigating the accumulation of cytotoxic superoxide radicals in TME.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Maira dos Santos Costa, Amanda de Camargo Faria, Rayssa L. Mota, Elena Gusevskaya
Summary: The study found that using green solvents as reaction media in palladium-catalyzed alkene oxidation reactions has better selectivity and faster reaction rates compared to traditional acetic acid solvents.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Multidisciplinary
Yuchan Han, Li Wu, Qi Han, Rongfan Zhang, Jun Li
Summary: Novel palladium-based catalysts were synthesized by attaching Pd(OAc)(2) to surface-modified mesoporous silica and graphene oxide. The physical and chemical properties of the catalysts were characterized. The stability of the catalyst and the heterogeneity of the reaction system were investigated through different approaches, and the performance of the catalyst SBA-15-B-Pd was found to be superior to that of GO-B-Pd. The catalysts could be reused multiple times without significant loss of performance.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Guoqi Zhang, Haisu Zeng, Shengping Zheng, Michelle C. Neary, Pavel A. Dub
Summary: The synthesis of branched Markovnikov's alcohols is crucial in the chemical industry. A highly regioselective hydroboration reaction using alkali metal triethylborohydrides as catalysts was discovered. This method allows for the selective and quantitative reduction of asymmetrical epoxides.
Article
Chemistry, Physical
Jonathan Trouve, Khalil Youssef, Sitthichok Kasemthaveechok, Rafael Gramage-Doria
Summary: Iron catalysts enable Markovnikov-selective reactions, achieving up to 99% selectivity for ketone products from (hetero)aromatic and aliphatic olefins under ambient conditions. The catalyst design, inspired by the promiscuous activity of cytochromes P-450 enzymes, allows the formation of iron-hydride species under catalytically relevant conditions, leading to the desired selectivity.
Article
Chemistry, Multidisciplinary
Zhiliang Huang, Renpeng Guan, Muralidharan Shanmugam, Elliot L. Bennett, Craig M. Robertson, Adam Brookfield, Eric J. L. McInnes, Jianliang Xiao
Summary: The oxidative cleavage of C = C double bonds with molecular oxygen is a key transformation in chemical and pharmaceutical synthesis. While nature has efficient enzymes for this reaction, synthetic chemists face challenges in finding suitable metal catalysts. This work presents a light-driven, Mn-catalyzed method for selective oxidation of alkenes with good functional group tolerance, involving asymmetric Mn-oxo species and methanol as an activator for O-2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mao Cai, Kaini Xu, Yuze Li, Zongxiu Nie, Long Zhang, Sanzhong Luo
Summary: The study presents a cooperative primary amine and ketone dual catalytic approach for the asymmetric alpha-hydroxylation of beta-ketocarbonyls with H2O2, achieving excellent yield and enantioselectivity. This cooperative amine/ketone catalytic approach provides a new strategy for the catalytic activation of H2O2 and expands the domain of typical amine and carbonyl catalysis to include this challenging transformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Tianze Xie, Robert M. Rioux
Summary: The text discusses the synthesis methods for incorporating light elements into the palladium lattice and their impact on catalytic properties, such as modifying electronic and geometric structures, in situ incorporation of hydrogen and oxygen, and their role in specific reactions.
Article
Chemistry, Physical
Sho Yamaguchi, Hiroki Kondo, Kohei Uesugi, Katsumasa Sakoda, Koichiro Jitsukawa, Takato Mitsudome, Tomoo Mizugaki
Summary: The study established a highly efficient catalytic system for converting biomass-derived alcohols into hydrocarbon fuels without the need for hydrogen gas. By using Pd/CeO2 catalyst, a wide range of alcohols were successfully converted into shorter carbon chain hydrocarbons with high yields. The catalyst was easily recoverable and reusable, making it a simple and sustainable method for producing hydrocarbon fuels from biomass-derived oxygenates.
Article
Chemistry, Multidisciplinary
Shu Fujita, Sho Yamaguchi, Jun Yamasaki, Kiyotaka Nakajima, Seiji Yamazoe, Tomoo Mizugaki, Takato Mitsudome
Summary: Alloying non-noble metal nanoparticles with phosphorus is a promising strategy for developing smart catalysts with high activity and air stability. For example, the novel nano-Ni2P catalyst exhibits excellent hydrogenation performance in water and can be easily reused without pretreatment.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Hiroya Ishikawa, Min Sheng, Ayako Nakata, Kiyotaka Nakajima, Seiji Yamazoe, Jun Yamasaki, Sho Yamaguchi, Tomoo Mizugaki, Takato Mitsudome
Summary: In this study, a supported cobalt phosphide nanoalloy catalyst was developed for the selective hydrogenation of furfural derivatives, showing high efficiency and air stability without the need for H-2 pretreatment. Backdonation from Co d-electrons to the pi* orbital of furfural derivatives was found to play a key role in the highly efficient hydrogenation process.
Article
Chemistry, Multidisciplinary
Min Sheng, Sho Yamaguchi, Ayako Nakata, Seiji Yamazoe, Kiyotaka Nakajima, Jun Yamasaki, Tomoo Mizugaki, Takato Mitsudome
Summary: An air-stable, active, and reusable non-noble-metal-based heterogeneous catalyst, hydrotalcite-supported cobalt phosphide nanorods (Co2P NR/HT), has been developed for the selective hydrogenation of nitriles to primary amines. The catalyst shows broad substrate generality and high activity under mild conditions, enabling nitrile hydrogenation with high yields without the need for ammonia.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Organic
Hang Xu, Sho Yamaguchi, Takato Mitsudome, Tomoo Mizugaki
Summary: In this study, the catalytic oxidative trimerization and oxygenative cleavage reactions of indoles were achieved using a copper nitride nanocube catalyst, producing valuable nitrogen-containing compounds such as indolin-3-ones and 2-ketoanilides under additive-free conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Hang Xu, Sho Yamaguchi, Takato Mitsudome, Tomoo Mizugaki
Summary: A simple and efficient hydroboration of alkynes using Cu3N NC catalyst has been reported for the first time. The catalyst allows the synthesis of vinyl boronate esters under mild reaction conditions without the need for additives or elevated temperatures. The Cu3N NCs can also be easily separated and reused, offering an environmentally friendly route for the production of vinyl boronates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Hiroya Ishikawa, Naoki Nakatani, Sho Yamaguchi, Tomoo Mizugaki, Takato Mitsudome
Summary: We report the use of ruthenium phosphide nanoparticles (Ru2P/SiO2) as a highly active and robust catalyst for the hydrogenation of sulfur-containing nitroarenes, with activity 34 times higher than that obtained with Ru nanoparticles. Various sulfur-containing nitroarenes were hydrogenated under 1 bar of H2, resulting in high yields of anilines, including important pharmaceutical intermediates. The electronic and geometrical effects of P surrounding Ru species in Ru2P/SiO2 were found to be crucial for enhancing the catalyst's activity and durability against sulfur poisoning.
Article
Multidisciplinary Sciences
Tomohiro Tsuda, Min Sheng, Hiroya Ishikawa, Seiji Yamazoe, Jun Yamasaki, Motoaki Hirayama, Sho Yamaguchi, Tomoo Mizugaki, Takato Mitsudome
Summary: Iron-based catalysts are advantageous metal catalysts due to their abundance and low toxicity. However, conventional iron nanoparticle catalysts have low activity in liquid-phase reactions and lack air stability. In this study, air-stable iron phosphide nanocrystal catalysts were developed to overcome the trade-off between activity and stability. These catalysts exhibited high activity for liquid-phase nitrile hydrogenation and can be immobilized on suitable supports for improved performance.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Hiroya Ishikawa, Naoki Nakatani, Sho Yamaguchi, Tomoo Mizugaki, Takato Mitsudome
Summary: We report the use of ruthenium phosphide nanoparticles (Ru2P/SiO2) as a highly active and robust catalyst for the hydrogenation of sulfur-containing nitroarenes, showing 34 times higher activity than Ru nanoparticles. Various sulfur-containing nitroarenes were successfully hydrogenated under 1 bar of H2, leading to high yields of aniline products, including valuable pharmaceutical intermediates. The study highlights the importance of the electronic and geometrical effects of P surrounding Ru species in Ru2P/SiO2 for enhanced activity and durability against sulfur poisoning.
Article
Chemistry, Physical
Saburo Hosokawa, Noriyuki Fukuzumi, Tetsu Nakatani, Tetsuo Honma, Tomoo Mizugaki, Tsunehiro Tanaka, Kenji Wada
Summary: The study demonstrates the selective synthesis of acetaldehyde by hydrogenation of acetic acid catalyzed by Pd-Fe alloy nanoparticles derived from Pd/Fe2O3. The optimal Pd loading amount (28-44 wt%) prevents the formation of iron carbides and leads to excellent acetaldehyde yield. In situ XAFS measurements show the reductive pretreatment of Pd/Fe2O3 forms core-shell type Pd-Fe alloy nanoparticles.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Katsumasa Sakoda, Sho Yamaguchi, Takato Mitsudome, Tomoo Mizugaki
Summary: A heterogeneous catalytic system Pt-Mo/ZrO2 was developed for the selective hydrodeoxygenation (HDO) of esters to synthesize unsymmetrical ethers. Under mild reaction conditions, a wide range of esters could be transformed into the corresponding unsymmetrical ethers. The Pt-Mo/ZrO2 catalyst also demonstrated successful conversion of a biomass-derived triglyceride into the corresponding triether. The cooperative catalysis between Pt nanoparticles and neighboring molybdenum oxide species on the ZrO2 surface played a key role in the highly selective HDO of esters. This catalyst system offers an efficient strategy for synthesizing unsymmetrical ethers and expands the scope of sustainable reaction processes.
Article
Chemistry, Multidisciplinary
Hiroya Ishikawa, Sho Yamaguchi, Ayako Nakata, Kiyotaka Nakajima, Seiji Yamazoe, Jun Yamasaki, Tomoo Mizugaki, Takato Mitsudome
Summary: This study demonstrates that phosphorus alloying significantly increases the deoxygenation activity of precious metal nanoparticles for sulfoxide conversion, and provides an efficient method to improve metal nanoparticle catalysis for diverse organic synthesis.
Article
Chemistry, Multidisciplinary
Min Sheng, Shu Fujita, Sho Yamaguchi, Jun Yamasaki, Kiyotaka Nakajima, Seiji Yamazoe, Tomoo Mizugaki, Takato Mitsudome
Summary: The study reported the successful synthesis of single-crystal cobalt phosphide nanorods containing coordinatively unsaturated Co-Co active sites, which serve as a new class of air-stable, highly active, and reusable heterogeneous catalysts for the reductive amination of carbonyl compounds. The air stability and high activity of the Co2P NRs is noteworthy, as conventional Co catalysts are air-sensitive and show no activity for this transformation under mild conditions. P-alloying is therefore of considerable importance for nanoengineering air-stable and highly active non-noble-metal catalysts for organic synthesis.
Article
Chemistry, Organic
Hang Xu, Sho Yamaguchi, Takato Mitsudome, Tomoo Mizugaki
Summary: Copper nitride nanoparticles act as efficient catalysts for hydroxylation reactions of aryl halides under ligand-free conditions, with the nitrogen atoms functioning as ligands to promote the reaction. The catalytic activity of Cu3N is comparable to conventional Cu catalysts with nitrogen ligands.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sho Yamaguchi, Shu Fujita, Kiyotaka Nakajima, Seiji Yamazoe, Jun Yamasaki, Tomoo Mizugaki, Takato Mitsudome
Summary: The study presents a non-noble metal catalyst, nickel phosphide nanoparticle supported on hydrotalcite, which effectively catalyzes the selective hydrogenation of d-glucose to d-sorbitol in water, with high yield and over 99% selectivity under mild conditions. This nano-Ni2P/HT catalyst shows superior activity compared to other non-noble metal catalysts, can operate at ambient temperature under just 1 bar of H-2, and is stable and reusable, providing a cheap, green, and sustainable route for the production of d-sorbitol.
