Article
Chemistry, Organic
Boxiang Liu, Zhicong Lin, Tairan Cheng, Tongxiang Cao, Shifa Zhu
Summary: In this study, a highly atom- and step-economical stereoselective synthesis of E-dienyl esters is reported. This approach involves rhodium catalysis and utilizes carboxylic acid and acetylene as C2 synthon through a cascade of cyclometalation and C-O coupling. The protocol demonstrates mild conditions, excellent functional group tolerance, exclusive E-stereoselectivity, and proves useful for late-stage modification of pharmaceuticals and natural products.
Article
Chemistry, Organic
Han Gao, Wujie Wang, Xiangying Lv, Gang Lu, Yuliang Li
Summary: The mechanism of Co(iii)-catalyzed annulation of N-chlorobenzamide with styrene was computationally studied, focusing on the effects of chiral cyclopentadienyl (Cp) ligands on enantioselectivity using energy decomposition analysis (EDA). The study revealed a spin-crossover event of Co complexes in the computed energy profile, with the triplet state of Co species being favored in most intermediates and transition states. The irreversible styrene migratory insertion was identified as the enantioselectivity-determining step, with steric effects being the dominant factor for high-level enantiocontrol, emphasizing the importance of additional bulky substituents on the Cp ring of trisubstituted BINOL-Cp ligands.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Bengi Ozgun Ozturk, Begum Sariaslan, Mina Askun, Zeynep Tunali, Solmaz Karabulut Sehitoglu
Summary: In this study, a sequential one-pot alkyne dimerization/hydration protocol was developed for the regioselective synthesis of alpha,beta-unsaturated ketones in quantitative yields. The reactions proceeded with high regioselectivity and rapid conversion, producing the corresponding unsaturated ketones within 15 minutes. Different arylacetylene derivatives could be efficiently converted to alpha,beta-unsaturated ketones in quantitative yields using this method.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Ana M. Geer, Janeth Navarro, Pablo Alaman-Valtierra, Nathan T. Coles, Deborah L. Kays, Cristina Tejel
Summary: Enhancing catalytic activity through synergic effects is a current challenge in homogeneous catalysis. In addition to the well-established metal-metal and metal-ligand cooperation, we showcase an example of self-activation by the substrate in controlling the catalytic activity of a two-coordinate iron complex. This behavior was observed in the regioselective cyclotrimerization of aryl acetylenes. Two kinetically distinct regimes were observed dependent upon the substrate-to-catalyst ratio, showing positive substrate cooperativity.
Article
Chemistry, Physical
Sagar Arepally, Ponnusamy Nandhakumar, Gisela A. Gonzalez-Montiel, Alina Dzhaparova, Gyeongho Kim, Ahyeon Ma, Ki Min Nam, Haesik Yang, Paul Ha-Yeon Cheong, Jin Kyoon Park
Summary: Electrochemical access to organometallic redox reagents allows for selective synthesis of various benzene derivatives with different regioisomers. A unified electrochemical strategy is presented for the selective cyclotrimerization of terminal alkynes to access both 1,3,5- and 1,2,4-regioisomeric trisubstituted benzene derivatives. The regiocontrol can be switched by the addition of a carboxylic acid.
Review
Chemistry, Organic
Padinjare Veetil Saranya, Mohan Neetha, C. M. A. Afsina, Gopinathan Anilkumar
Summary: Multicomponent reactions (MCRs) can form highly functionalized compounds through the reaction between three or more reactants in a one-pot manner, providing products with the utilization of lesser resources and energy. MCRs adhere to the principles of green chemistry and have diverse applications across various fields.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: This study presents a rhodium-catalyzed electrochemical reaction for the selective synthesis of structurally diverse hexasubstituted arenes. The method demonstrates excellent selectivity and high atom economy.
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: A cooperative rhodium-catalyzed electrochemical 1,3-butadiyne [2 + 2 + 2] cyclotrimerization is presented, which selectively produces hexasubstituted arenes. The method features high selectivity, good functional group tolerance, and high atom economy.
Article
Chemistry, Multidisciplinary
John M. Halford-McGuff, David B. Cordes, Allan J. B. Watson
Summary: A Rh-catalyzed [2+2+2] cycloaddition approach for the synthesis of BMIDA-functionalized arenes is developed to address the reactivity issues associated with internal alkynes. The method enables the access to highly functionalized borylated benzene scaffolds, and exhibits broad functional group compatibility and high yields. The utility of the products is demonstrated through their elaboration and synthesis of fused heterocycles via intramolecular Chan-Lam etherification and amination. The dominance of sterically controlled reactivity is described.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Jiang-Tao Fan, Xin-Heng Fan, Cai-Yan Gao, Jinchao Wei, Lian-Ming Yang
Summary: The simple catalytic system of Ni(PPh3)(2)Cl-2/dppb or dppm/Zn shows efficient and regioselective control in alkyne cyclotrimerization reactions, demonstrating practical potential for the construction of complex benzene derivatives. Preliminary mechanistic studies have been conducted.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Steve Huvelle, Pascal Matton, Christine Tran, Marie-Noelle Rager, Mansour Haddad, Virginie Ratovelomanana-Vidal
Summary: A convenient method for the ruthenium-catalyzed synthesis of benzo[c]naphthyridinone derivatives has been reported. The method shows high yields and regioselectivity, and is applicable to a wide range of substrates.
Article
Chemistry, Multidisciplinary
Maximilian Sender, Fabian L. Huber, Maximilian C. G. Moersch, Daniel Kowalczyk, Julian Hniopek, Sarah Klingler, Michael Schmitt, Simon Kaufhold, Kevin Siewerth, Juergen Popp, Boris Mizaikoff, Dirk Ziegenbalg, Sven Rau
Summary: This work elaborates on the effect of dynamic irradiation on light-driven molecular water oxidation and emphasizes the importance of overall reaction engineering in overcoming limiting factors. By controlling the local availability of photons, the overall catalytic efficiency can be significantly enhanced.
Article
Chemistry, Organic
Jeremy R. Tuck, Robert J. Tombari, Noah Yardeny, David E. Olson
Summary: In this study, arylazo-1,2,3-triazoles were successfully synthesized using azide-alkyne click chemistry, showcasing high thermal stabilities and near-quantitative bidirectional photoconversion.
Article
Chemistry, Organic
Nidhi Mishra, Sumit K. Singh, Anoop S. Singh, Anand K. Agrahari, Vinod K. Tiwari
Summary: Glycosyl triazoles are efficient ligands for Cu-catalyzed Sonogashira reaction, overcoming challenges of sideways homocoupling reactions. High product yields can be achieved at 130 degrees C for various substrates, showing versatility of this catalytic system.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Li-Hsiang Wang, Juntaro Nogami, Yuki Nagashima, Ken Tanaka
Summary: We have successfully synthesized axially chiral figure-eight spiro[9.9]-cycloparaphenylene (CPP) tetracarboxylates with high enantioselectivity (up to 75:25 er) via the cationic Rh-(I)/(R)-H-8-BINAP complex-catalyzed chemo-, regio-, and enantioselective intermolecular double [2 + 2 + 2] cycloaddition reaction of an achiral symmetric tetrayne with dialkyl acetylenedicarboxylates followed by reductive aromatization. The spiro[9.9]-CPP tetracarboxylates exhibit distorted structure with large dihedral and boat angles at the phthalate moieties and show weak aggregation-induced emission enhancement behavior.
Review
Chemistry, Physical
Victorio Cadierno
Review
Chemistry, Physical
Victorio Cadierno
Editorial Material
Chemistry, Physical
Victorio Cadierno
Review
Chemistry, Organic
Vittorio Cadierno
Summary: Recent developments in the metal-catalyzed hydrofunctionalization of alkynes with carboxylic acids are comprehensively reviewed in this study, with a focus on both inter- and intramolecular processes and their implications in the synthesis of natural products and biologically active molecules. This review also highlights the use of cascade processes for the assembly of complex heterocyclic compounds.
CURRENT ORGANIC CHEMISTRY
(2021)
Editorial Material
Chemistry, Physical
Victorio Cadierno
Review
Chemistry, Inorganic & Nuclear
Sergio E. Garcia-Garrido, Alejandro Presa Soto, Eva Hevia, Joaquin Garcia-Alvarez
Summary: This Minireview challenges the conventional wisdom by focusing on recent advances in using s-block organometallic reagents under air, at room temperature, and in the presence of moisture. The success of these approaches relies on the use of sustainable solvents and has been demonstrated for various organic transformations. The choice of solvent is crucial in affecting the constitution of s-block organometallic species in solution.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Victorio Cadierno
Summary: Metal-catalyzed hydrofunctionalization reactions of alkynes, especially conjugated 1,3-diynes, have been extensively studied. These reactions provide a straightforward and efficient route to functionalized olefins and various heterocyclic and carbocyclic compounds. However, the regio- and stereocontrol issues associated with conjugated 1,3-diynes make the hydrofunctionalization reactions challenging.
Article
Chemistry, Organic
Javier Francos, Victorio Cadierno
Summary: This study presents a new synthetic procedure for obtaining two previously reported donor-acceptor butadiene dyes. The reactions proceed in water under MW irradiation and the target products were characterized using various analysis methods.
Review
Chemistry, Physical
Pascale Crochet, Victorio Cadierno
Summary: N-Heterocyclic carbenes (NHCs) are widely used ligands in organometallic chemistry and catalysis due to their stability and flexibility. By functionalizing NHCs with hydrophilic groups, they can be used in aqueous catalysis, which is a hot topic in Green Chemistry. This review summarizes the research on hydrophilic NHC-gold catalysts and the catalytic applications of water-soluble gold nanoparticles stabilized by hydrophilic NHCs.
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)
Review
Chemistry, Inorganic & Nuclear
Pascale Crochet, Victorio Cadierno
Summary: This review article focuses on the catalytic applications of arene-osmium(II) complexes, discussing transfer hydrogenation, hydrogenation, oxidation, and nitrile hydration reactions, as well as different C-C bond forming processes comprehensively, showing that they can achieve comparable or superior effectiveness in some instances compared to their ruthenium analogues.
Article
Chemistry, Organic
Rebeca Gonzalez-Fernandez, Pascale Crochet, Victorio Cadierno
Summary: The title compound was synthesized by electrophilic cyanation of commercially available (R)-4-chloro-alpha-methylbenzylamine, yielding a yellow oil in 84% yield. It was characterized using various methods such as H-1 and C-13{H-1] NMR, IR, HRMS, and specific rotation measurements.
Article
Chemistry, Organic
Javier Francos, Alba E. Diaz-Alvarez, Victorio Cadierno
Article
Chemistry, Physical
Rebeca Gonzalez-Fernandez, Daniel Alvarez, Pascale Crochet, Victorio Cadierno, M. Isabel Menendeze, Ramon Lopez
CATALYSIS SCIENCE & TECHNOLOGY
(2020)
