Review
Chemistry, Multidisciplinary
Li-Jie Cheng, Neal P. Mankad
Summary: Transition metal-catalyzed carbonylation reactions are an effective method to introduce oxygen functionality into organic compounds. However, challenges such as the use of noble metals as catalysts and the reactivity of certain substrates remain.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Physical
Nikita Kvasovs, Valeriia Iziumchenko, Vitalii Palchykov, Vladimir Gevorgyan
Summary: This method utilizes visible light-induced generation of nucleophilic hybrid alkyl Pd radical intermediates to achieve efficient atom economical C-C bond construction of alkyl-substituted oximes, allowing a broad range of primary, secondary, and tertiary alkyl bromides and iodides, as well as a range of different formaldoximes, to efficiently undergo this transformation.
Article
Chemistry, Organic
Swantje Lerch, Stefan Fritsch, Thomas Strassner
Summary: This study reports the use of TAAILs as solvents in the Mizoroki-Heck reaction. By optimizing the reaction conditions, efficient synthesis of (E)-stilbene derivatives with high yields was achieved. The catalytic system using TAAILs showed higher yields compared to other commercially available ionic liquids.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ziyan Zhang, Nikita Kvasovs, Anastasiia Dubrovina, Vladimir Gevorgyan
Summary: This method utilizes visible light-induced and Bronsted acid-assisted generation of hybrid palladium C(sp(3))-centered radical intermediate, enabling efficient transformation of a wide range of vinyl arenes, heteroarenes, and diazo compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kitty K. Asahara, Kei Muto, Junichiro Yamaguchi
Summary: A Pd-catalyzed denitrative intramolecular Mizoroki-Heck reaction of nitroarenes with alkenes has been developed, providing a convergent synthetic method for benzo-fused cyclic compounds.
Article
Polymer Science
Ameneh Ahmadi, Tahereh Sedaghat, Roya Azadi
Summary: In this study, a Palladium-based magnetic nanocomposite was synthesized and utilized as a catalyst for Suzuki coupling and Heck-Mizoroki coupling reactions, demonstrating efficient catalytic activity and recyclability.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2021)
Article
Chemistry, Physical
Xiao-Qing Han, Lei Wang, Ping Yang, Jing-Yuan Liu, Wei-Yan Xu, Chao Zheng, Ren-Xiao Liang, Shu-Li You, Junliang Zhang, Yi-Xia Jia
Summary: A palladium-catalyzed intramolecular enantioselective Mizoroki-Heck reaction of naphthalenes has been developed, leading to the formation of a series of unique heterocyclic compounds with enantiomeric excess values retained. The reaction relies on the use of a chiral sulfonamide phosphine ligand to inhibit competitive and undesired reactions.
Article
Chemistry, Physical
Ayat Nuri, Abolfazl Bezaatpour, Mandana Amiri, Nemanja Vucetic, Jyri-Pekka Mikkola, Dmitry Yu Murzin
Summary: Mesoporous SBA-15 silicate was prepared by a hydrothermal method, modified with organic melamine ligands, and used for deposition of Pd nanoparticles for Mizoroki-Heck coupling reactions. The optimized reaction parameters allow for efficient recovery and reuse of the catalyst.
Article
Chemistry, Multidisciplinary
Vladimir Burilov, Ramilya Garipova, Diana Mironova, Elza Sultanova, Ilshat Bogdanov, Evgeny Ocherednyuk, Vladimir Evtugyn, Yuri Osin, Ildar Rizvanov, Svetlana Solovieva, Igor Antipin
Summary: A new imidazolium amphiphilic calix[4]arene with terminal acetylene fragments was synthesized and covalently cross-linked under CuAAC conditions in water. The obtained polymeric particles showed enhanced performance as a support for Pd(OAc)2 in the Mizoroki-Heck reaction, especially in water.
Article
Chemistry, Physical
Elizaveta V. Larina, Anna A. Kurokhtina, Elena V. Vidyaeva, Nadezhda A. Lagoda, Alexander F. Schmidt
Summary: The study focused on the role of ionic Pd species in catalytic systems for cross-coupling reactions, specifically investigating the differential selectivity of the Mizoroki-Heck reaction with competition between aryl halides or alkenes. It was found that the additives of tertiary phosphine and halide salts significantly affect the catalytic activity of anionic Pd complexes, determining the regioselectivity of the reaction.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Organic
Giuseppe Dilauro, Luciana Cicco, Paola Vitale, Filippo Maria Perna, Vito Capriati
Summary: Deep eutectic solvent, choline chloride/glycerol, has been proven to be an effective and sustainable reaction medium for the synthesis of valuable tetrahydrofuran and tetrahydropyran derivatives. The reaction proceeds under aerobic conditions, without the need for additional ligands, and has a good substrate scope.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Subba Rao Polimera, Andivelu Ilangovan, Murugaiah A. M. Subbaiah
Summary: Silyl enol ethers were used as a masked source of saturated ketones for the synthesis of β-aryl enones and their derivatives. Through dehydrosilylation and oxidative arylation using arylboronic acids, these compounds were generated in situ using a one-pot relayed Pd-(II) catalysis under base-free conditions. Oxygen was found to be an effective oxidant for both dehydrosilylation and arylation reactions. The arylation conditions could be customized to utilize aryl halides as an alternative source of arylating agents. The study investigated the preparative scope using 35 examples with yields up to 95%, and mechanistic studies suggested a cationic Pd-(II)-based catalytic system.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Xiaopeng Peng, Yang Yang, Bingling Luo, Shijun Wen, Peng Huang
Summary: A diverse set of fluorenes can be conveniently constructed starting from cyclic diaryliodoniums and terminal alkenes through Pd-catalyzed reactions. These reactions involve a conventional Mizoroki-Heck reaction and a reductive Heck reaction, with a general scope of alkenes leading to the synthesis of 29 fluorenes, expanding the structural diversity of fluorenes.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Rajagopal Anbarasan, Kesavan Nithya, Basuvaraj Suresh Kumar, Devarajan Suresh, Arlin Jose Amali
Summary: A well-defined heterogeneous catalyst, Pd nanoparticles incorporated on SiO2 nanocapsules, Pd@SiO2 NCs, is synthesized and demonstrated to be a competent and selective catalyst in Mizoroki-Heck reactions and epoxidation reactions on Mizoroki-Heck coupled products. The Pd@SiO2 NCs exhibit unaltered catalytic efficiency, mild and sequential reaction conditions with TON up to 183, and a wide substrate scope. The porosity developed by the self-assembled SiO2 NPs and the functionality imparted by the glucose moiety to entrap Pd nanoparticles result in structurally stable and recyclable catalytic sites with no loss of activity.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Polymer Science
Liting He, Yunhai Yu, Fujia Liu, Junpo He
Summary: In this study, substituted poly(phenylacetylene)s were synthesized through Mizoroki-Heck coupling reaction using α-bromostyrene derivatives as monomers. K2CO3 was found to be an effective base, while Et3N showed little catalytic reactivity. Kinetic study showed that electron withdrawing group on the phenyl ring increased the polymerization rate of the corresponding monomer. Additionally, incorporating aryl and vinyl halides into a single vinyl monomer allowed the synthesis of branched polyacetylene with oligo(phenylene vinylene) at the branch points. This approach provides a new tool for the molecular engineering of substituted polyacetylene materials.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Chemistry, Applied
Yi-Ting Wang, Yi-Lun Shih, Yen-Ku Wu, Ilhyong Ryu
Summary: Site-selective C(sp(3))-H alkenylation was achieved under photo-irradiation in the presence of a catalytic decatungstate anion. The reaction successfully combines radical addition/beta-scission sequence with photocatalytic C(sp(3))-H functionalization. The decatungstate anion participates in a chain-repairing step in reactions with weaker C-H bonds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Takayoshi Kasakado, Takahide Fukuyama, Tomohiro Nakagawa, Shinji Taguchi, Ilhyong Ryu
Summary: This study reports the high-speed C-H chlorination of ethylene carbonate and introduces a photoflow setup for gas-liquid biphasic reactions. The direct use of chlorine gas and the photoirradiation conditions affect the selectivity of the product.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Takahide Fukuyama, Takayoshi Kasakado, Mamoru Hyodo, Ilhyong Ryu
Summary: In this article, we discuss the effectiveness of photo-induced organic reactions when using evolving photo flow technologies. By updating the flow reactors and light sources, the energy profile of the reactions improved significantly. We successfully applied photo flow technologies in various reactions, such as isomerization, alkylation, radical cyclization, and oxidation.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2022)
Article
Chemistry, Analytical
Mamoru Hyodo, Hitomi Iwano, Takayoshi Kasakado, Takahide Fukuyama, Ilhyong Ryu
Summary: High-power UV-LED irradiation effectively accelerated the decatungstate-anion-catalyzed oxidation reaction of benzyl alcohol, leading to increased yield and selectivity of benzoic acid. The combination of a flow photoreactor and high-power irradiation reduced the reaction time to minutes.
Article
Chemistry, Applied
Takashi Kuwahara, Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: The RuHCl(CO)(PPh3)(3)-catalyzed cross-coupling reaction has been extended to synthesize 1,3-diaryl 1,3-diketones, and also applied to the synthesis of PPT (propyl pyrazole triol). A study revealed the formation of a five-membered ruthenacycle, beta-ruthenium ketone, during the reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Shuhei Sumino, Lhyong Ryu
Summary: The radical polymerization of methyl acrylate in the presence of a palladium dimer complex under photoirradiation conditions led to the formation of poly(methyl acrylate) with good D values. The polymerization process could be controlled by switching the light on and off, exhibiting living characteristics. It is proposed that alpha-Pd polyesters could act as dormant species and generate transient alpha-keto radicals and persistent Pd radicals upon photoirradiation.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Organic
Yi-Lun Shih, Yen-Ku Wu, Mamoru Hyodo, Ilhyong Ryu
Summary: A catalytic amount of decatungstate photocatalyst under black light irradiation was able to promote the oxidative cleavage of C=C bonds with molecular oxygen, resulting in the formation of both aromatic and aliphatic ketones. The use of a high-power ultraviolet light-emitting diode at 365 nm for the continuous flow reaction of alpha-methylstyrene significantly reduced the reaction time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Baptiste Picard, Takahide Fukuyama, Ilhyong Ryu
Summary: An improved carbonylation method for amide bond formation between aryl iodides and aromatic amines is presented, which does not require a phosphine ligand unlike conventional Pd catalysis. The catalyst system consists of bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). This method allows the synthesis of various aromatic amides and can be scaled to gram order synthesis under low carbon monoxide pressure.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shuhei Sumino, Ilhyong Ryu
Summary: The radical bromoallylation of alkynes, allenes, and vinylidene cyclopropanes can proceed efficiently in the presence of a radical initiator to give different diene derivatives. Three-component reactions involving allenes, electron-deficient alkenes, and allyl bromides can provide good yields of 1,7-dienes. The reaction of arylalkenes with allyl bromides can selectively produce 5-bromoalkenes, while the bromoallylation of vinylcyclopropanes results in 5-exo ring closure to yield 1-(bromomethyl)-2-vinylcyclopentane derivatives with high yields. All of the products contain a reactive vinyl bromide moiety, which can be easily functionalized through Pd-catalyzed cross-coupling and radical cascade reactions.
Review
Chemistry, Physical
Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: This paper summarizes our team's efforts over the past two decades in the development of new catalytic methods for C-C bond formation. The versatile applications of the commercially available catalyst RuHCl(CO)(PPh3)(3) (or RuH for short) are highlighted through eight different transformations. The fundamental steps involved in the catalysis are emphasized, demonstrating how our mechanistic understanding and the diverse catalytic capabilities of RuH can be utilized to design desired catalytic cycles and develop new cross-coupling reactions with high atom-economy.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Applied
Takahide Fukuyama, Takashi Kuwahara, Yuki Yamamoto, Baptiste Picard, Ilhyong Ryu
Summary: The selective olefin isomerization of homoallyl silyl ethers and carbonates was investigated by utilizing RuHCl(CO)(PPh3)(3) as the catalyst. It was found that the presence of an aryl or alkyl substituent at the α-position to the oxygen atom led to selective conversion to allyl silyl ethers, while no substituent at the α-position resulted in isomerization to enol silyl ethers. In contrast, the isomerization of homoallyl carbonates gave the corresponding allyl carbonates selectively regardless of the substituent at the α-position.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Chen-Yang Tsai, Yin-Jia Jhang, Yen-Ku Wu, Ilhyong Ryu
Summary: This study reports a protocol for alkene hydroxyalkenylation and a photocatalytic protocol for alkoxyalkenylation. Alkenes can be converted into the corresponding 1-phenylsulfonyl-4-hydroxyalkenes or alkoxyalkenes in good to high yields using a persulfate anion as an oxidation reagent and 1,2-bis(phenylsulfonyl)ethylene as a radical acceptor. The methods exhibit wide substrate adaptability and regioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nobukazu Taniguchi, Mamoru Hyodo, Lin-Wei Pan, Ilhyong Ryu
Summary: Site-selective C(sp(3))-H thiolation has been achieved using thiosulfonates as substrates and the decatungstate anion as a photocatalyst. The reaction proceeds through a cascade of double S(H)2 reactions, HAT and ArS group transfer, and PCET, allowing the recovery of the catalyst, W10O324-.
CHEMICAL COMMUNICATIONS
(2023)
Article
Polymer Science
Ryo Takabayashi, Stephan Feser, Hiroshi Yonehara, Ilhyong Ryu, Takahide Fukuyama
Summary: In this study, it was found that nitroxide-mediated radical polymerization (NMP) using BlocBuilder MA under continuous flow reaction conditions led to higher conversions and smaller polydispersity index (D) values compared to batch reaction conditions. The addition of a small amount of acetol or malononitrile accelerated the NMP reaction without sacrificing the quality of the polymer. Flow reactors allowed for precise control of the NMP process initiated by BlocBuilder MA and the synthesis of di-block copolymers.
Review
Chemistry, Multidisciplinary
Takuji Kawamoto, Takahide Fukuyama, Baptiste Picard, Ilhyong Ryu
Summary: This feature article highlights the powerful methods of radical carbonylation and our current efforts in developing new strategies for this reaction.
CHEMICAL COMMUNICATIONS
(2022)
