Article
Chemistry, Multidisciplinary
Hyo-Jun Lee, Keiji Maruoka
Summary: This article provides detailed insights into the applications of four types of amino Tf-amide catalysts in asymmetric transformations, including stereoselective reactions catalyzed by enamine intermediates, asymmetric direct Mannich reactions catalyzed by aliphatic Tf-amides, asymmetric direct aldol reactions and conjugate additions catalyzed by primary-amino aliphatic Tf-amides, and asymmetric transformations catalyzed by modified amino aromatic Tf-amides.
Article
Chemistry, Physical
Ming-Sheng Xie, Ning Li, Yin Tian, Xiao-Xia Wu, Yun Deng, Gui-Rong Qu, Hai-Ming Guo
Summary: A study reported the use of bifunctional chiral PPY N-oxides as catalysts for dynamic kinetic resolution of racemic carboxylic esters, achieving high yields and enantioselectivity for the synthesis of chiral alpha-aryl alpha-alkyl carboxylic esters. Mechanistic studies revealed the crucial role of oxygen atoms in PPY N-oxides during the reaction process.
Article
Chemistry, Multidisciplinary
Glen Kai Bin Kua, Giang Kien Truc Nguyen, Zhi Li
Summary: This study reports a novel enzymatic amidation concept in an aqueous system, which involves the glycerol activation of fatty acids and their subsequent aminolysis with glycine to synthesize N-acyl glycines. The enzyme proRML was engineered to enhance its aminolysis activity and catalytic efficiency, leading to high yields of N-lauroylglycine and other N-acyl glycines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Shuoqi Zhang, Rong Gu, Shigeyoshi Sakaki, Guixiang Zeng
Summary: The mechanism of the N-N cross-coupling of nitroarene and aniline catalyzed by 1,2,2,3,4,4-hexamethylphosphetane oxide (1PO) was investigated using DFT and DLPNO-CCSD(T) calculations. The study revealed the formation of active species 1P through deoxygenation of 1PO and the extraction of one oxygen atom from nitroarene to produce nitrosoarene. The formation of azo-cation intermediate and stable hydrazinylphosphonium species were also identified. The study proposed that substitution of a dimethylamino group for the methyl group in 1P could improve its activity.
Article
Chemistry, Multidisciplinary
Daniel Rozsar, Alistair J. M. Farley, Iain McLauchlan, Benjamin D. A. Shennan, Ken Yamazaki, Darren J. Dixon
Summary: This article describes the enantioselective intermolecular conjugate addition of nitroalkanes to unactivated alpha,beta-unsaturated esters catalyzed by a bifunctional iminophosphorane (BIMP) superbase. It provides a straightforward approach to the synthesis of pharmaceutically relevant enantioenriched gamma-nitroesters with unprecedented selectivity. The methodology demonstrates broad substrate scope and has been successfully applied on a gram scale with reduced catalyst loading, allowing for catalyst recovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Hongwei Gao, Wenkai Cao, Jinmei He, Yongping Bai
Summary: A high-performance biaxially oriented PET film (BOPETA) is prepared by incorporating 4 mol% amide units formed by 1,12-dodecanediamine and terephthalic acid, which enhances interchain forces through the formation of hydrogen bonds. The BOPETA film exhibits improved crystallinity and mechanical properties, as well as lower water and oxygen permeabilities compared to BOPET. Additionally, the optical properties of the BOPETA film remain good after incorporating amide units, with a light transmittance of 88.8% and slight anti-UV performance. This work discusses a simple approach for preparing PET films with good mechanical strength, high transparency, and improved gas barrier properties for packaging.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Organic
Azusa Kondoh, Sho Yamaguchi, Yushi Watanabe, Masahiro Terada
Summary: A catalytic addition reaction between allyl sulfones and α,β-unsaturated ketones was developed using a phosphazene base as the catalyst. This reaction efficiently proceeds, which is a rare example of a catalytic addition reaction of β-acylvinyl anion equivalents, and a preliminary study on asymmetric variant was conducted.
Article
Chemistry, Physical
Ming-Sheng Xie, Meng Shan, Ning Li, Yang-Guang Chen, Xiao-Bing Wang, Xuan Cheng, Yin Tian, Xiao-Xia Wu, Yun Deng, Gui-Rong Qu, Hai-Ming Guo
Summary: An efficient chiral 4-aryl-pyridine-N-oxide (ArPNO) nucleophilic organocatalyst was designed, synthesized, and successfully applied in the dynamic kinetic resolution of azoles, aldehydes, and anhydrides, providing high yields, excellent enantioselectivity, and structural diversity. Mechanistic studies revealed the key role of acyloxypyridinium cation formation and the higher nucleophilic ability of oxygen in pyridine-N-oxide, contributing to the development of diverse chiral 4-substituted pyridine-N-oxides as efficient nucleophilic organocatalysts.
Article
Chemistry, Organic
Shaofeng Li, Hanyu Nie, Mengyan Duan, Wenfei Wang, Congjun Zhu, Chuanjun Song
Summary: This work presents a strategy for the one-pot synthesis of protoberberine alkaloid derivatives using palladium catalyzed cascade alpha-arylation and cyclization, resulting in moderate to excellent isolated yields. The protocol provides an efficient and convenient path to multisubstituted protoberberine derivatives and can directly yield natural alkaloids.
Article
Chemistry, Multidisciplinary
Yuanyuan Ping, Xiao Li, Qi Pan, Wangqing Kong
Summary: Ligand-directed divergent synthesis is a strategy that can transform common starting materials into distinct molecular scaffolds. This strategy enables the rapid construction of structurally rich collection of small molecules for biological evaluation and reveals novel modes of catalytic transformation, representing one of the most sought-after challenges in synthetic chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Wen-Ran Zhang, Wen-Wen Zhang, Huanrong Li, Bi-Jie Li
Summary: Despite recent progress in asymmetric hydrosilylation, achieving metal-catalyzed enantioselective hydrosilylation of unactivated internal alkenes remains challenging. In this study, we demonstrate a rhodium-catalyzed enantioselective hydrosilylation of unactivated internal alkenes bearing a polar group. The coordination assistance provided by an amide group enables the reaction to proceed with high regio- and enantioselectivity.
Article
Chemistry, Organic
Hanbin Lu, Jiamin Lv, Canhua Zhou, Mi Zhou, Yanxiong Fang, Jinxiang Dong, Terumasa Kato, Yan Liu, Keiji Maruoka
Summary: In this study, a catalytic asymmetric direct Michael reaction of ketones with trans-beta-arylnitroethenes was successfully achieved under the influence of optically pure L-hydroxyproline-based secondary-amino aromatic Tf-amide organocatalyst. The addition of trialkylamine base additives, such as diethylmethylamine, played a crucial role in achieving high reactivity and enantioselectivity in this asymmetric Michael reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Qing Gu, Zhi-Jie Wu, Shu-Li You
Summary: Enantioselective C-H addition is a straightforward and efficient method for synthesizing optically active molecules from readily available arenes. Different types of chiral catalysts can achieve enantioselective C-H addition reactions with various substrates, providing a direct access to valuable chiral fragments. The reaction mechanisms of these enantioselective C-H additions are also introduced in this review.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Organic
Cheng Chun-Xia, Wu Lu-Ping, Sha Feng, Wu Xin-Yan
Summary: An organocatalytic enantioselective direct vinylogous allylic alkylation between coumarins and racemic Morita-Baylis-Hillman carbonates has been developed, achieving a wide range of densely functionalized coumarin derivatives with high yields (87% to 99%) and high enantioselectivity (up to 98% ee) using 10 to 15 mol% chiral cyclohexane-based phosphine-amide C10 as the catalyst.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Eun-Sol Choi, Hee-Chan Jeong, Ye-Lin Han, Hyo-Jun Lee, Keiji Maruoka
Summary: A novel activation method using a hypervalent iodine(III) reagent and Selectfluor is developed for esters with a non-activated cyclopropyl moiety, resulting in the generation of acyl fluorides. These acyl fluorides, versatile synthetic intermediates, can be smoothly transformed into various carbonyl compounds, especially amides. This method can also be applied to selective activation of diester compounds.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wanderson C. de Souza, Bianca T. Matsuo, Priscilla M. Matos, Jose Tiago M. Correia, Marilia S. Santos, Burkhard Koenig, Marcio W. Paixao
Summary: N-Alkyl-N-(2-(1-arylvinyl)aryl)cinnamamides can be converted into natural product inspired scaffolds via iridium photocatalyzed intramolecular [2+2] photocycloaddition, allowing the synthesis of a variety of tetrahydrocyclobuta[c]quinolin-3(1H)-ones with high molecular complexity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jose Tiago M. Correia, Marilia S. Santos, Emanuele F. Pissinati, Gustavo P. da Silva, Marcio W. Paixao
Summary: In the past decade, visible-light photocatalysis has been proven to be a powerful tool for constructing N-heterocyclic frameworks, which are important components of natural products, insecticides, pharmacologically relevant therapeutic agents and catalysts. This account highlights recent advancements and established methods in photocatalytic cascades for preparing various classes of N-heterocycles, with a focus on the author's contributions to the field.
Article
Chemistry, Organic
Wanderson C. Souza, Jose Tiago M. Correia, Priscilla M. Matos, Camila M. Kisukuri, Pablo S. Carneiro, Marcio W. Paixao
Summary: This study presents a new approach for the synthesis of 1,3-diene derived quinolinone compounds using a mild reaction protocol, a metal-free catalyst, and a sustainable solvent. The methodology offers an efficient route towards decorated 1,3-diene products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Lenna Rosanie Cordero Mallaupoma, Barbara Karina de Menezes Dias, Maneesh Kumar Singh, Rute Isabel Honorio, Myna Nakabashi, Camila de Menezes Kisukuri, Marcio Weber Paixao, Celia R. S. Garcia
Summary: Melatonin can synchronize the intraerythrocytic cycle of the parasite by triggering a specific signaling cascade. Compounds with certain chemical structures have inhibitory effects on the proliferation of malaria parasites, indicating their potential as new antimalarial drugs. The study found that certain synthetic compounds can inhibit different chloroquine-resistant strains of the parasite. In addition, melatonin affects the parasite load and modulates the expression of signaling components, providing a focus for further research.
Article
Chemistry, Applied
Saul Alberca, Marta Velazquez, Jose Trujillo-Sierra, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, David Monge
Summary: Catalysts generated by combinations of Pd(TFA)(2) and pyridine-hydrazone ligands have been successfully applied to the addition of arylboronic acids to aliphatic N-carbamoyl hydrazones, providing protected alpha-aryl monoalkylhydrazines with high enantioselectivities. The resulting monosubstituted hydrazines can serve as key building blocks for the synthesis of various organic compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Organic
Guilherme A. M. Jardim, Juliana A. Dantas, Amanda A. Barboza, Marcio W. Paixao, Marco A. B. Ferreira
Summary: Visible-light-induced palladium-mediated reactions have shown great potential in organic synthesis and can achieve new and unique reactivities by generating versatile Pd-radical hybrid species. This review provides an overview of recent advances in the combination of Pd-based photocatalytic manifolds and radical generation in the functionalization of important motifs in synthetic chemistry.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Wanderson C. C. de Souza, Rafaely N. N. Lima, Iva S. S. de Jesus, Jose Tiago M. Correia, Marcio W. Paixao
Summary: A deaminative alkyl radical cascade cyclization of 1,7-dienes under visible-light photocatalysis is reported. This method enables the synthesis of a family of benzoazepinones (benzazepinones) and can be carried out under mild reaction conditions, providing a broad substrate scope with excellent functional group tolerance and good yields. This protocol has also been extended to 1,7-enynes, resulting in a representative collection of cyclopentaquinolinones.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Kimberly Benedetti Vega, Jose Antonio Campos Delgado, Lucas V. B. L. Pugnal, Burkhard Koenig, Jose Tiago Menezes Correia, Marcio Weber Paixao
Summary: In this study, a strategy for the precise installation of sulfones and carboxylic acids onto styrenes using sodium sulfinates and CO2 as coupling partners was described. The protocol allowed for the preparation of carboxy-sulfonylated compounds with high yields and broad functional group tolerance. Additionally, a one-pot photocatalytic carboxy-sulfonylation-elimination strategy was developed for the synthesis of alpha-aryl-acrylates by taking advantage of the leaving group ability of the sulfone moiety.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Pilar Elias-Rodriguez, Esteban Matador, Manuel Benitez, Tomas Tejero, Elena Diez, Rosario Fernandez, Pedro Merino, David Monge, Jose M. Lassaletta
Summary: Modulable monosulfonyl squaramides activate gold(I) chloride complexes through H bonding in an intermolecular way. The combination of (PPh3)AuCl or IPrAuCl complexes with an optimal sulfonyl squaramide cocatalyst efficiently catalyzes various heterocyclizations and a cyclopropanation reaction. Computational studies reveal that the Au-Cl bond breaks through transligation to the triple bond in a ternary complex formed by the AuCl center dot center dot center dot HBD catalyst and the substrate.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Pilar Elias Elias-Rodriguez, Esteban Matador, Manuel Benitez, Tomas Tejero, Elena Diez, Rosario Fernandez, Pedro Merino, David Monge, Jose M. Lassaletta
Summary: Modulable monosulfonyl squaramides activate gold(I) chloride complexes through H-bonding. Combinations of (PPh3)AuCl or IPrAuCl complexes and an optimal sulfonyl squaramide cocatalyst efficiently catalyze heterocyclizations and a cyclopropanation reaction, while avoiding undesired side reactions. Computational studies suggest that the Au-Cl bond breaks by transligation to the triple bond in a ternary complex formed by the AuCl...HBD catalyst and the substrate.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Muhammad Saeed Ahmad, Abu Bakar Siddique, Muhammad Khalid, Akbar Ali, Muhammad Ashraf Shaheen, Muhammad Nawaz Tahir, Muhammad Imran, Ahmad Irfan, Muhammad Usman Khan, Marcio Weber Paixao
Summary: In this study, a one-pot synthesis of tetra-substituted imidazole was reported, and a series of metal complexes were obtained by reacting the synthesized imidazole with salts of 1(st) row transition metals. The synthesized compounds were characterized using spectroscopic and analytical techniques, and their antioxidant and antimicrobial activities were evaluated. The results showed that the metal complexes exhibited stronger antimicrobial activity compared to the ligand, and the ligand had better antioxidant activity than the metal complexes. Computational studies revealed a clear intra-molecular charge transfer in the ligand and its metal complexes.
Review
Chemistry, Multidisciplinary
Bianca T. Matsuo, Pedro H. R. Oliveira, Emanuele F. Pissinati, Kimberly B. Vega, Iva S. de Jesus, Jose Tiago M. Correia, Marcio Paixao
Summary: This review summarizes the latest advances in the preparation of amide-containing compounds using carbamoyl radicals. The application of photoinduced protocols provides a range of structurally relevant derivatives. The study also discusses a recent approach using photolytic C-S cleavage of dithiocarbamate-carbamoyl intermediates.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Odette Concepcion, Francisco J. Penaloza, Jhon Jairo Lopez, Gustavo Cabrera-Barjas, Claudio A. Jimenez, Marcio W. Paixao, Alexander F. de la Torre
Summary: This study presents a simple method for synthesizing N-alkylated peptides and depsipeptides containing olefins, which can be achieved through sequential one-pot protocol of multicomponent reaction and oxidative elimination. The regioselective construction of alpha,beta-dehydrobutyrine and alpha,beta-dehydro-homophenylalanine was possible using Ugi four-component reaction, while the Passerini three-component reaction produced beta-enamide preferably.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Attilio Chiavegatti Neto, Kelly Cintra Soares, Maiara da Silva Santos, Tulio Jardini Aimola, Antonio Gilberto Ferreira, Guilherme A. M. Jardim, Claudio Francisco Tormena, Marcio Weber Paixao, Marco Antonio Barbosa Ferreira
Summary: Here, a fully detailed mechanistic study on the organocatalyzed metal-free click reactions for the synthesis of 1,2,3-triazoles is reported. The elementary steps, intermediates, and transition states of the reactions are investigated using DFT calculations and H-1 NMR monitoring experiments, providing detailed profiles for both reaction mechanisms. DIAS analysis is also employed to elucidate the regioselectivity in these reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Sancler C. Vasconcelos, Lucas Marchini, Carolina G. S. Lima, Vinicius G. C. Madriaga, Ruan S. A. Ribeiro, Vinicius Rossa, Luanne E. M. Ferreira, Fernando de C. da Silva, Vitor F. Ferreira, Fabio Barboza Passos, Rajender S. Varma, Marcio W. Paixao, Thiago M. Lima
Summary: The development of efficient and green catalytic strategies for biomass upgrading is crucial. Single-atom catalysts and single-atom alloys have shown promising potential in overcoming issues associated with conventional catalytic approaches, and their application in biomass valorization is rapidly growing. This article provides an overview of the preparation, characterization, and catalytic evaluation of single-atom catalysts and alloys in biomass upgrading reactions, along with a critical outlook on the topic.