Review
Chemistry, Applied
Xiaofan Cui, Remi Chauvin, Chao Pi, Yangjie Wu, Xiuling Cui
Summary: This review presents recent progress in the use of vinylene carbonate as a reactant in transition metal-catalyzed C-H bond activation/cyclization reactions. By analyzing and comparing different reaction models, it highlights the advantages of using vinylene carbonate as a surrogate for ethynol and other reactants, and discusses related mechanisms and synthetic applications.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Ramanna Jatoth, Praveen Kumar Naikawadi, Boyapally Bhaskar, Kishan Gugulothu, Peramalla Edukondalu, K. Shiva Kumar
Summary: Metal-free TFA promoted arylation/heteroarylation was achieved under mild conditions via the reaction of chloro-derivatives of nitrogen heterocycles with electron rich arenes/heteroarenes. It was also observed that TFA was able to facilitate other reactions, resulting in the formation of fused N-heterocycles.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Carmine Lops, Paolo Pengo, Lucia Pasquato
Summary: The highly basic and poorly nucleophilic phosphazene base P-1-t-Bu promotes the Darzens condensation of alpha-halo esters with aromatic aldehydes to afford alpha,beta-epoxy esters in nearly quantitative yields under mild and short reaction time conditions. The more basic P-4-t-Bu phosphazene is useful for low reactivity aldehydes. These reactions can be performed in low polarity organic solvents to minimize hydrolysis of the alpha,beta-epoxy esters.
Review
Chemistry, Organic
Lona Dutta, Atanu Mondal, S. S. V. Ramasastry
Summary: The reductive aldol reaction (RAR) is important in forming carbon-carbon bonds. Various methods have been developed utilizing RAR as a key step to access complex molecular frameworks. The literature on metal-free reductive aldol chemistry is discussed in this overview.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Rosalin Bhanja, Shyamal Kanti Bera, Prasenjit Mal
Summary: The increasing concerns about global warming have led to a surge in demand for sustainable energy sources in the field of synthetic organic chemistry. The development of mild synthetic strategies for generating heterocyclic compounds, particularly those containing boron, has gained significant attention due to their wide-ranging applicability. This comprehensive review aims to collect literature on light-induced borylation reactions, specifically focusing on photocatalyst-free and transition metal-free methodologies. The emphasis is on exploring selective mechanistic investigations to elucidate the substantial potential of eco-friendly approaches in synthesizing heterocyclic compounds and advancing sustainable organic chemistry. The catalyst-free photoinduced approach represents a green energy alternative and has gained prominence in contemporary synthesis.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Ryo Tsunokawa, Yukiko Karuo, Atsushi Tarui, Kazuyuki Sato, Takaaki Hosoya, Tomohiro Agou, Kentaro Kawai, Masaaki Omote
Summary: Metal-free pyridine arylations have been achieved using O-triflated pyridine N-oxides and N-alkylated indoles. The reactions proceed through reactive intermediates activated by Tf2O treatment, which allow for the selective installation of various indoles at the nitrogen-adjacent positions of pyridine. This protocol offers mild conditions, short reaction times, and ease of handling, making it an environmentally friendly approach to pyridine arylation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Rofin Mangali, Sengodagounder Muthusamy
Summary: This study demonstrates the BF3-catalyzed S-H insertion reactions of alpha-diazo imidamides and various substituted thioureas/thiosemicarbazones/cyclic thioamides to afford the corresponding S-H insertion products. The method exhibits wide substrate applicability and resistance to moisture and air, with moderate to excellent yields.
NEW JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
Laxmidhar Rout, Tharmalingam Punniyamurthy
Summary: Arylboron and arylphosphorus compounds are important structures in synthetic chemistry for constructing complex molecules. Transition-metal-mediated C-B and C-P cross-couplings are powerful tools for synthesizing these compounds, allowing for the functionalization of reactive aryl halides. Efforts have been made to expand the scope of these reactions to include carboxylic acid derivatives and the functionalization of C-F and C-H bonds.
COORDINATION CHEMISTRY REVIEWS
(2021)
Review
Chemistry, Organic
Preeti, Krishna Nand Singh
Summary: This report highlights the progress and advantages of metal-free multicomponent reactions in synthesizing moncyclic six-membered N-heterocycles, including pyridine, pyrimidine, pyrazine, triazine and their hydrogenated derivatives. The literature since 2000 not only offers diverse methods for synthesis of these heterocycles, but also provides new insights into the exploration of metal-free multicomponent chemistry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Rui Zhang, Chang-Yang Song, Zhe Sui, Ye Yuan, Yu-Cheng Gu, Cheng Chen
Summary: Carbon-heteroatom bond formation without transition metals is a powerful synthetic method for efficiently synthesizing valuable molecules. This review presents selected examples and discusses the construction of C-N (including amination and amidation) and C-O (including etherification and hydroxylation) bonds under transition-metal free conditions. The involved catalysts/promoters, substrate scope, potential applications, and reaction mechanisms are systematically discussed.
Article
Chemistry, Inorganic & Nuclear
Chuting Zhang, Lijuan Peng, Bohou Song, Zhiwen Li, Xiaoqun Cao
Summary: A sustainable catalyst system for Sonogashira cross-coupling reaction was developed using nanoporous palladium as the catalyst. The catalyst remained stable and active over multiple cycles without significant leaching or loss of activity, and high yields of the desired alkynes were obtained.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Ya-Nan Li, Bin Wang, Ye-Kai Huang, Jin-Song Hu, Jia-Nan Sun
Summary: This mini-review summarizes the current knowledge and recent advances since 2017 in the synthetic utility of electrochemical transformations for the C-H functionalization of nitrogen-containing heterocycles.
FRONTIERS IN CHEMISTRY
(2022)
Review
Chemistry, Organic
Pratiksha Bhorali, Sabera Sultana, Sanjib Gogoi
Summary: This review article highlights the recent advances in metal-catalyzed C-H functionalization of sulfoxonium ylides, emphasizing their importance as carbene-transfer agents and their advantages over other counterparts.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xi Cheng, Da-Bin Qin, Zhi-Bing Dong
Summary: An efficient three-component synthesis of disubstituted 4-aryl-2-aminothiazoles was reported. The protocol features transition-metal free, short reaction time, easily available starting materials, good yields, and broad substrate scope, showing potential synthetic value for the synthesis of a variety of biological or pharmaceutical active compounds.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Atsushi Ohtaka
Summary: Over the past few decades, the use of transition metal nanoparticles in catalysis, particularly in C-C bond forming reactions, has attracted significant attention. Through the use of various stabilizers, a wide range of metal nanoparticles with high catalytic activity for C-C bond forming reactions have been developed.
Article
Chemistry, Multidisciplinary
Yuki Takada, Joaquim Caner, Hiroshi Naka, Susumu Saito
PURE AND APPLIED CHEMISTRY
(2018)
Article
Multidisciplinary Sciences
Lyu-Ming Wang, Yuna Morioka, Kellie Jenkinson, Andrew E. H. Wheatley, Susumu Saito, Hiroshi Naka
SCIENTIFIC REPORTS
(2018)
Correction
Multidisciplinary Sciences
Lyu-Ming Wang, Yuna Morioka, Kellie Jenkinson, Andrew E. H. Wheatley, Susumu Saito, Hiroshi Naka
SCIENTIFIC REPORTS
(2018)
Article
Biochemistry & Molecular Biology
Takato Hara, Hiroko Tatsuishi, Tomomi Banno, Tomoya Fujie, Chika Yamamoto, Hiroshi Naka, Toshiyuki Kaji
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2018)
Article
Chemistry, Multidisciplinary
Tomoya Kanda, Asuka Naraoka, Hiroshi Naka
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Organic
Lyu-Ming Wang, Kensuke Kobayashi, Mitsuhiro Arisawa, Susumu Saito, Hiroshi Naka
Article
Chemistry, Organic
Hiroyuki Okabe, Asuka Naraoka, Takahiro Isogawa, Shunsuke Oishi, Hiroshi Naka
Article
Chemistry, Organic
Asuka Naraoka, Hiroshi Naka
Article
Chemistry, Organic
Hiroshi Naka, Asuka Naraoka
TETRAHEDRON LETTERS
(2020)
Article
Chemistry, Organic
Huatai Liang, Zhurong Li, Yan Liu, Sei Murayama, Hiroshi Naka, Keiji Maruoka
Summary: This research successfully synthesized optically pure, deuterated D-4-Simplified Maruoka Catalyst and deuterated D-2-Simplified Maruoka Catalyst, and compared their chemical reactivity with the original Simplified Maruoka Catalyst.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Sei Murayama, Zhurong Li, Huatai Liang, Yan Liu, Hiroshi Naka, Keiji Maruoka
Summary: Site-specifically deuterated organocatalysts exhibit enhanced reactivity compared to non-deuterated analogs in the asymmetric catalytic alkylation of amino acid derivatives. The stability of phase-transfer catalysts can be improved by site-specific deuteration, with a significant secondary kinetic isotope effect observed for tetradeuterated catalysts. These findings suggest that catalyst deuteration is a promising strategy to enhance the stability and performance of organocatalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Shogo Mori, Shu Sakurai, Hiroshi Naka, Susumu Saito
Summary: In this paper, our research on metal-loaded semiconductor-photocatalyzed organic transformations using alcohols over the past decade is reviewed. Unlike many reactions that only use alcohols as sacrificial electron donors, our study has demonstrated the use of alcohols as valuable organic building blocks for the synthesis of value-added products. In addition to discussing previous results, our ongoing project involving photocatalytic C-C bond-forming reactions via C-C bond scission of tertiary alcohols is briefly introduced.
Article
Chemistry, Organic
Yuki Hashiba, Shogo Mori, Ivven Huang, Yuna Morioka, Hiroshi Naka, Susumu Saito
Summary: A photocatalytic system using metal-loaded titanium dioxide in methanol under near-UV light irradiation is reported for the efficient N-methylation of a-amino acids and peptides. The method allows for the N-methylation of twenty different a-amino acid motifs found in proteins in the human body, regardless of the polar/non-polar or acidic/basic functional groups present in the substrates. Dipeptides can also undergo N-methylation at the N-terminal while maintaining the integrity of the peptide bond and carboxylic acid. Most of the N-methylated products can be easily isolated through simple filtration and concentration, eliminating the need for tedious purification processes such as aqueous workup and column chromatography.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Moeko Itoga, Masako Yamanishi, Taro Udagawa, Ayane Kobayashi, Keiko Maekawa, Yoshiji Takemoto, Hiroshi Naka
Summary: The development of chemoselective C(sp(3))-H deuteration is of great interest. In this study, the alpha-selective, iridium(iii)-bipyridonate-catalyzed hydrogen(H)/deuterium(D) isotope exchange of alcohols using deuterium oxide (D2O) as the primary deuterium source is reported. This method enables the direct deuteration of primary and secondary alcohols under basic or neutral conditions without being affected by coordinative functional groups such as imidazole and tetrazole. Successful substrates for deuterium labeling included losartan potassium, rapidosept, guaifenesin, and diprophylline. The deuterated losartan potassium showed higher stability towards the metabolism by CYP2C9 than the protiated analogue. Kinetic and DFT studies indicated that the direct deuteration proceeds through dehydrogenation of alcohol to the carbonyl intermediate, conversion of [Ir-III-H] to [Ir-III-D] with D2O, and deuteration of the carbonyl intermediate to give the alpha-deuterated product.
Article
Chemistry, Multidisciplinary
Yuki Wada, Toshiki Akiyama, Kazuo Harada, Tetsuo Honma, Hiroshi Naka, Susumu Saito, Mitsuiro Arisawa
Summary: The novel platinum nanoparticle catalyst PtNP/TiO2, closely located near the surface of titanium oxide, exhibits environmentally friendly catalytic activity for the synthesis of ethers from benzyl alcohols under the wavelength of 420 nm by combining the properties of a photocatalyst and a metal nanoparticle catalyst.
