Article
Chemistry, Organic
Jun Li, Zhi-Wen Zhao, Shuang Zheng, Ping He, Ji-Ying Qiu, Quan-Quan Zhou, Zhi-Lin Ren
Summary: Herein, we describe a novel one-pot method for the synthesis of polysubstituted pyrrole derivatives via a three-component reaction of alkenyl bromides, amines, and isocyanides. The conversion process is catalyzed by a Pd catalyst without the need for additional ligands. The key feature of this method is the orderly insertion of three isocyanide molecules, directed by the intramolecular imine group. Additionally, DFT calculations provide support for the proposed reaction mechanism.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Ting Zhou, Yuqi Zhu, Hong Zhang, Jieyin He, Hongguang Li, Ming Lang, Jian Wang, Shiyong Peng
Summary: A one-pot tandem annulation of 1,6-allenynes with organic azides was reported using copper catalysis and TsOH promotion, providing N-allyl 1,2,3-triazole-fused structures in moderate to excellent yields under mild reaction conditions. Additionally, the N-allyl products can be further diversified by selectively reducing them to the N-alkyl counterparts.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Masayuki Kubo, Naomi Inayama, Eisuke Ota, Junichiro Yamaguchi
Summary: Dance reactions on aromatic rings provide a powerful tool in organic chemistry to move functional groups. By combining with transition-metal-catalyzed coupling reactions, dance reactions of halides and pseudohalides offer a unique platform for the synthesis of diverse substituted aromatic compounds.
Review
Chemistry, Physical
Maria Teresa Herrero, Jokin Diaz de Sarralde, Nerea Conde, Aitor Herran, Garazi Urgoitia, Raul SanMartin
Summary: Cascade reactions provide a direct pathway to valuable compounds and simplify synthetic sequences. The cascade reaction between alkynoic acids and aminonucleophiles, catalyzed by metal catalysts, is a powerful tool for the construction of nitrogen-containing heterocyclic compounds. This review discusses the literature on metal-catalyzed cascade reactions, including substrate-catalyst ratio, aminonucleophile properties, substrate scope, and alternative solvents.
Article
Chemistry, Organic
Hyemin Kang, Seunghwan An, Sunwoo Lee
Summary: An efficient iron-photocatalyzed approach was developed for the double decarboxylative coupling of alkynoic acids and alkyl carboxylic acids, providing easy access to alkylated alkynes. The Fe(NO3)3 & BULL;9H2O or FeCl2/TPA catalyst exhibited good activity under blue light conditions in the presence of PhI(OAc)2, showing good functional-group tolerance and activity towards primary, secondary, and tertiary alkyl carboxylic acids. Under the iron-photocatalytic system, the double decarboxylative coupling of alkynoic acids and alkyl carboxylic acids yielded alkylated alkynes in good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jokin Diaz de Sarralde, Elene Astobieta, Ania Sevilla, Yuliet Rincon, Maria Teresa Herrero, Garazi Urgoitia, Raul SanMartin
Summary: With the scarcity of chemical resources, catalysis by first-row transition metals has gained increasing interest. Iron, due to its abundance, low toxicity, and unique electronic features, holds promise. In this study, quinazoline alkaloids were synthesized from alkynoic acids and functionalized amines using iron dibromide and pyridine as catalysts in toluene or a solventless reaction system. The study focused on iron sources, reaction media, and the effect of additives. Results showed high yields and regioselective preparation of nitrogen- and oxygen-containing scaffolds. This is the first example of a cascade process involving alkynoic acids catalyzed by iron. Compared to previously reported gold, copper, and ruthenium catalysts for similar transformations, iron is more abundant, cheaper, and less toxic.
ENVIRONMENTAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Rahul K. Shukla, Akshay M. Nair, Chandra M. R. Volla
Summary: Recent years have witnessed the development of transition metal catalyzed C-H activation as a powerful method in organic synthesis. Allene reactivity has attracted considerable interest among synthetic chemists. Although directing group assisted C(sp(2))-H functionalization with allenes has been well studied, coupling with more challenging aliphatic C(sp(3))-H bonds remains a challenge. Here, we report a Pd(ii) catalyzed aliphatic C(sp(3))-H dienylation using allenyl acetates directed by 8-aminoquinoline. A wide range of carboxylic acids, including fatty acids and amino acids, were effectively functionalized at the beta and gamma positions to provide diversely functionalized 1,3-dienes. Preliminary mechanistic studies suggest that the success of this transformation relies on the crucial role of the base. The reaction proceeds through regioselective 2,3-migratory insertion of the allene with the alkylpalladium(ii) species followed by beta-acetoxy elimination.
Article
Chemistry, Physical
Carlos J. Moreno, Karel Hernandez, Simon J. Charnok, Samantha Gittings, Michael Bolte, Jesus Joglar, Jordi Bujons, Teodor Parella, Pere Clapes
Summary: Three enzymatic routes have been reported for the synthesis of gamma-hydroxy-alpha-amino acids through tandem aldol addition-transamination reactions. The resulting chiral molecules can be further transformed into valuable chiral alpha-amino-gamma-butyrolactones, which are important intermediates for pharmaceutical synthesis.
Article
Chemistry, Organic
Jian Tang, Fengjie Lu, Yujie Geng, Yanxia Liu, Ensheng Zhang
Summary: An efficient and straightforward approach for site-selective functionalization of phenylalanine and phenylalanine-containing peptide has been developed via a Pd-catalyzed tandem reaction. The method allows for dual C-H activation, including C-C coupling with benzoquinone and intramolecular C-N cyclization, providing a rapid and feasible synthetic route to incorporate 4-benzoquinone-indoline fragments into peptides.
Article
Chemistry, Multidisciplinary
Abdelkarim El Qami, Badr Jismy, Ahmed El Hakmaoui, Mohamed Akssira, Mohamed Abarbri
Summary: An efficient one-pot regioselective synthesis of 2-(1,2,3-triazolyl)methyl-3-alkynyl imidazo[1,2-a]pyridines is reported, yielding new imidazo[1,2-a]pyridines embedded with 4-substituted-[1,2,3]-triazole in good to excellent yields under mild reaction conditions via a one-pot sequence involving SN reaction with azide, copper-catalyzed [3+2] cycloaddition, and Sonogashira coupling reaction.
Review
Chemistry, Multidisciplinary
Bing Xu, Quanpu Wang, Chao Fang, Zhan-Ming Zhang, Junliang Zhang
Summary: This review summarizes the latest advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years. The review is organized into thirteen sections based on the different types of transformations involved. Chiral palladium catalysts have shown outstanding features in promoting a plethora of enantioselective cyclization reactions, providing convenient access to structurally diverse chiral carbo- and hetero-cycles.
CHEMICAL SOCIETY REVIEWS
(2023)
Review
Chemistry, Physical
Linda Z. Nikoshvili, Valentina G. Matveeva
Summary: This review discusses the recent progress in Pd-catalyzed tandem processes, focusing on homogeneous and heterogeneous catalysts as well as metal-enzyme catalysts. It covers various types of tandem reactions and their applications in fine organic synthesis and biotechnology.
Article
Chemistry, Organic
Xiyan Rui, Chao Wang, Dongjuan Si, Xuechao Hui, Keting Li, Hongmei Wen, Wei Li, Jian Liu
Summary: This reaction method is simple and efficient, allowing for the preparation of phenothiazine products from readily available starting materials, with high atom economy and broad substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Bijin Li, Mazen Elsaid, Haibo Ge
Summary: C(sp(3))-H functionalization is an important method to increase molecular complexity. Despite the initial challenges of inertness and high bond-dissociation energies, these hurdles can be overcome through selective strategies, leading to efficient construction of C-C and C-X bonds. This review discusses transition-metal-catalyzed site-selective gamma- and delta-C(sp(3))-H functionalization reactions and explores their applications in late-stage functionalization of medicinal compounds and construction of complex molecules of medicinal importance.
Review
Chemistry, Multidisciplinary
Laura M. Wickham, Ramesh Giri
Summary: Alkene dicarbofunctionalization is a powerful organic synthesis method that utilizes transition metals and carbon sources to synthesize complex molecules. The strategy of cyclometalation and metallacycle contraction is employed to address the issue of beta-H elimination in alkene dicarbofunctionalization reactions.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Review
Chemistry, Multidisciplinary
Paolo Destito, Cristian Vidal, Fernando Lopez, Jose L. Mascarenas
Summary: Developing non-natural biocompatible transformations in biologically relevant media has attracted significant interest in the past decade, with the use of transition metal complexes offering unique possibilities. This translation of metal catalyst potential to biological environments poses challenges, but describing the most relevant advances and key challenges helps identify issues from an organometallic perspective.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Andrea F. Quivelli, Giovanna D'Addato, Paola Vitale, Joaquin Garcia-Alvarez, Filippo M. Perna, Vito Capriati
Summary: An efficient protocol for synthesizing tertiary alcohols via nucleophilic addition has been developed, with high yields of up to 98%. The method demonstrates broad substrate scope and can be conducted under environmentally friendly conditions.
Article
Chemistry, Multidisciplinary
David Elorriaga, Felipe de la Cruz-Martinez, Maria Jesus Rodriguez-Alvarez, Agustin Lara-Sanchez, Jose Antonio Castro-Osma, Joaquin Garcia-Alvarez
Summary: The rapid addition of highly polar organometallic reagents to cyclic carbonates has been studied, allowing for the synthesis of highly substituted tertiary alcohols, beta-hydroxy esters, or symmetric ketones without the need for isolation or purification of any reaction intermediates.
Article
Chemistry, Multidisciplinary
Andrea Francesca Quivelli, Manuela Marino, Paola Vitale, Joaquin Garcia-Alvarez, Filippo M. Perna, Vito Capriati
Summary: The efficient protocol developed for Cu-catalyzed Ullmann-type aryl alkyl ether synthesis demonstrates high yield production of desired products, valorization of cheap polyols, and successful recycling of catalyst, base, and solvent multiple times.
Article
Chemistry, Multidisciplinary
David Elorriaga, Blanca Parra-Cadenas, Antonio Antinolo, Fernando Carrillo-Hermosilla, Joaquin Garcia-Alvarez
Summary: The study demonstrated the efficient and selective fast addition of in situ generated lithium amides into carbodiimides or nitriles in ethereal green solvents, allowing for the successful synthesis of guanidines or amidines under air/moisture at room temperature without the need for isolation or purification of any halfway reaction intermediate. This environmentally-friendly protocol shows potential for applied synthesis of highly-substituted iminic-type fine chemical products.
Article
Chemistry, Multidisciplinary
Javier A. Cabeza, Jose M. Fernandez-Colinas, Joaquin Garcia-Alvarez, Pablo Garcia-Alvarez, Carlos J. Laglera-Gandara, Marina Ramos-Martin
Summary: A family of germyl rhodium complexes derived from the PGeP germylene have been synthesized and their reactivity and applications have been studied.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Andrea Francesca Quivelli, Federico Vittorio Rossi, Paola Vitale, Joaquin Garcia-Alvarez, Filippo Maria Perna, Vito Capriati
Summary: A sustainable and efficient two-step methodology for the synthesis of Thenfadil has been developed, utilizing a combination of reductive amination and Cu-catalyzed C-N coupling reactions in environmentally responsible deep eutectic solvents. Under optimized conditions, both reactions proceed smoothly with good yields and suppression of side products. A simplified workup procedure and the potential for scale-up and synthesis of analogs have also been demonstrated.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
David Elorriaga, Fernando Carrillo-Hermosilla, Blanca Parra-Cadenas, Antonio Antinolo, Joaquin Garcia-Alvarez
Summary: This study investigated the synthesis of highly selective asymmetric tertiary alcohols under the absence of external organic solvents. It was found that the reaction can be carried out at room temperature and under air/moisture, without the need for a protecting atmosphere. The results showed high chemoselectivity and the possibility of scaling up the protocol.
Article
Chemistry, Multidisciplinary
Luciana Cicco, Marianna Roggio, Marcos Lopez-Aguilar, Marina Ramos-Martin, Filippo Maria Perna, Joaquin Garcia-Alvarez, Paola Vitale, Vito Capriati
Summary: An efficient, selective, and sustainable catalytic method has been developed for the oxidation of activated alcohols to the corresponding carbonyl compounds. The reaction proceeds under mild conditions and yields high product yields.
Article
Biochemistry & Molecular Biology
Andrea Francesca Quivelli, Federico Vittorio Rossi, Chiara Alario, Francesco Sannicolo, Paola Vitale, Joaquin Garcia-Alvarez, Filippo Maria Perna, Vito Capriati
Summary: The use of eco-friendly solvents 2-MeTHF and CPME in the synthesis of dimethindene was found to reduce environmental impact, increase synthesis yield, and simplify manual operations.
Article
Chemistry, Multidisciplinary
Maria J. Rodriguez-Alvarez, Sergio E. Garcia-Garrido, Serena Perrone, Joaquin Garcia-Alvarez, Vito Capriati
Summary: The use of Deep Eutectic Solvents (DESs) as reaction media for transition-metal-catalyzed organic transformations has gained significant interest in the past decade. These solvents, derived from renewable and non-toxic precursors, offer advantages such as easy recyclability and compatibility with heterogeneous catalysis. Recent studies have demonstrated the efficient coupling of transition-metal-based nanoparticles with DESs in various synthetic protocols, including coupling reactions, oxidation/reduction processes, heterocycle synthesis, and polymerization reactions.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Marina Ramos-Martin, Nicolas Rios-Lombardia, Javier Gonzalez-Sabin, Sergio E. Garcia-Garrido, Carmen Concellon, Alejandro Presa Soto, Vicente del Amo, Joaquin Garcia-Alvarez
Summary: This research demonstrates the use of Fe-III-based deep eutectic mixture as both promoter and solvent for the selective hydration of alkynes under mild conditions. Ligands, co-catalysts, or co-solvents are not required.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Marina Ramos-Martin, Nicolas Rios-Lombardia, Javier Gonzalez-Sabin, Sergio E. Garcia-Garrido, Carmen Concellon, Alejandro Presa Soto, Vicente del Amo, Joaquin Garcia-alvarez
Summary: An efficient, simple and general protocol for the selective hydration of terminal alkynes has been developed using a cheap and sustainable FeIII-based eutectic mixture as both promoter and solvent. The reaction can take place under mild conditions and in the absence of additional ligands or toxic metals. The obtained methyl ketones can be easily isolated without the use of VOC solvents and the FeIII-based eutectic mixture can be recycled multiple times.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Davide Arnodo, Marina Ramos-Martin, Luciana Cicco, Vito Capriati, Nicolas Rios-Lombardia, Javier Gonzalez-Sabin, Alejandro Presa Soto, Joaquin Garcia-Alvarez
Summary: The highly efficient biodeoximation of aromatic ketoximes, promoted by the enzymatic oxidative system laccase/TEMPO/O-2, has been successfully combined with the fast and chemoselective addition of highly-polar s-block organometallic reagents (RLi/RMgX), resulting in the synthesis of highly-substituted tertiary alcohols. This one-pot tandem protocol enables the selective synthesis of tertiary alcohols under mild reaction conditions without the need for intermediate isolation/purification steps.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Marina Ramos-Martin, Ramon Lecuna, Luciana Cicco, Paola Vitale, Vito Capriati, Nicolas Rios-Lombardia, Javier Gonzalez-Sabin, Alejandro Presa Soto, Joaquin Garcia-Alvarez
Summary: The combination of enzymes and polar organometallic chemistry in aqueous media allows for the straightforward and chemoselective synthesis of tertiary alcohols with broad substrate scope and excellent conversions, demonstrating the efficiency and potential applications of this novel approach.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
