Article
Chemistry, Physical
Damien B. Culver, James M. Boncella
Summary: New (RPNP)-P-H ligands containing 2,4-xylyl (4mXPN(H)P) and mesityl (MesPN(H)P) groups on the phosphorus atoms were synthesized. These ligands reacted with ruthenium complexes to form various complexes with different reactivities. The activation of ortho methyl groups and the formation of transient amide complexes were observed. These complexes show potential as catalysts for dehydrogenative coupling reactions.
Article
Chemistry, Physical
Jasnoor S. Mann, Binh Khanh Mai, Thanh Vinh Nguyen
Summary: The carbonyl-alkyne metathesis (CAM) reaction is a versatile method to access alpha,beta-unsaturated carbonyl compounds, which are important precursors and structural motifs in biologically active substances. We developed an efficient organic Lewis acid catalytic system that promotes both intramolecular and intermolecular CAM reactions. Our metal-free protocol can produce a diverse family of useful organic structures from a broad range of substrates.
Article
Chemistry, Multidisciplinary
Zibo Bai, Heng Zhang, Hao Wang, Hanrui Yu, Gong Chen, Gang He
Summary: An enantioselective addition reaction of various alkyl groups to unactivated internal alkenes under Cu catalysis has been developed, leading to high yields of β-lactams featuring two contiguous stereocenters with excellent enantioselectivity. Mechanistic studies suggest that a nucleophilic addition of the alkyl radical to Cu-II-coordinated alkene is the enantio-determining step.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Yuki Kojima, Yuji Nishii, Koji Hirano
Summary: A copper-catalyzed regio- and stereoselective allylboration reaction has been developed to functionalize 1-trifluoromethylalkenes with bis(pinacolato)diboron and allylic chlorides, resulting in high diastereoselective trifluoromethylated products. The success of this reaction relies on the careful selection of Cs2CO3 base and t-Bu-modified dppe-type ligand, which allows for efficient catalyst turnover and suppression of defluorination side reactions. The resulting Bpin moiety can be derivatized to provide diverse CF3-containing molecules with high stereochemical fidelity.
Article
Chemistry, Physical
Apakorn Phasuk, Ricardo B. B. Metz
Summary: The interaction between aluminum cations and acetone in the gas phase was studied using photodissociation vibrational spectroscopy. The spectra of Al+(acetone)(N-2) and Al+(acetone)( n ) (n = 2-5) ions were measured and compared to DFT calculated vibrational spectra to determine the structures of the complexes. The experiments showed red shift of the C=O stretch and blue shift of the CCC stretch, which decreased as the size of the clusters increased. The calculations predicted that the most stable isomer for n ≥ 3 was pinacolate, where oxidation of Al+ enabled reductive C-C coupling between two acetone ligands. Experimentally, pinacolate formation was observed for n = 5, as evidenced by a new peak at 1185 cm(-1) characteristic of the pinacolate C-O stretch.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Organic
Hong Li, Rongqiang Tian, Zheng Duan
Summary: A facile and highly atom-economic approach to 2-phosphafurans was reported in this study, with the key step utilizing the Lewis acidity of electrophilic phosphinidenes to induce an intramolecular cyclization with enones. Dearomative hetero-Diels-Alder reactions of 2-phosphafurans provided two series of bicyclic phosphacycles, representing a rare synthetic application of the Lewis acidity of electrophilic phosphinidene complexes in phosphinidene chemistry.
Article
Chemistry, Organic
Shuai Liu, Yi-Sen Qian, Jian-Lin Xu, Lei Xu, Yun-He Xu
Summary: A three-component coupling method was reported for the regio- and stereoselective difunctionalization of allenes with allenyl ethers, bis(pinacolato)diboron, and gem-dichlorocyclobutenones as electrophiles, leading to highly functionalized cyclobutenone products tethering with an alkenylborate fragment. The polysubstituted cyclobutenone products also showed diverse transformation abilities.
Article
Chemistry, Multidisciplinary
Trixia M. Buscagan, Kathryn A. Perez, Ailiena O. Maggiolo, Douglas C. Rees, Thomas Spatzal
Summary: CO can bind to the FeMo-cofactor of nitrogenase and is both an inhibitor and substrate, undergoing reduction to hydrocarbons. A crystal structure study revealed two CO ligands coordinated to the FeMo-cofactor, suggesting privileged roles for Fe2 and Fe6 in ligand binding with multiple coordination modes available.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Alison L. Lambright, Yanyao Liu, Isaac A. Joyner, Kaitlyn M. Logan, M. Kevin Brown
Summary: The method utilizes amide-directed nickel catalysis to achieve highly selective synthesis of cyclopentane scaffolds containing boronic ester and amide functional groups. The nature of the amide directing group influences the reaction outcome, leading to predictably selective reactions based on the solvent and base counterion.
Article
Chemistry, Organic
Tuong Anh To, Binh Khanh Mai, Thanh Vinh Nguyen
Summary: This article reports a new Bronsted acid-catalyzed carbonyl-olefin metathesis reaction using nitromethane as a solvent, which can promote intramolecular ring-closing reactions.
Article
Chemistry, Multidisciplinary
Hefei Yang, Le-Cheng Wang, Yu Zhang, Dongling Zheng, Zhengkai Chen, Xiao-Feng Wu
Summary: A substrate-controlled regioselective functionalization of unactivated alkenes with trifluoroacetimidoyl chlorides has been developed to synthesize structurally diverse trifluoromethyl-containing indoles and indolines. The regioselectivity of the reaction is determined by the structure of the alkene substrates.
Article
Chemistry, Organic
Bendu Pan, Xu Qian, Yaqi Zhang, Long Jiang, Rihui Cao, Liqin Qiu
Summary: An iridium-catalyzed intramolecular asymmetric allylic etherification of pyrimidine methanols using chiral-bridged biphenyl phosphoramidite ligand L3 and triethylborane resulted in the synthesis of a class of novel pyrimidine-fused oxazepanes with up to 99% yield and 99.5% enantiomeric excess. This work addresses the challenge of insufficient nucleophilicity of aliphatic alcohols and demonstrates the vital value of chiral-bridged biphenyl phosphoramidites. The multifunctional transformations of the products further showcase the robust synthetic utility of this methodology.
Article
Chemistry, Multidisciplinary
Gemma L. Parker, Ruben Van Lommel, Nil Roig, Mercedes Alonso, Adrian B. Chaplin
Summary: A spectroscopic and computational examination of a series of rhodium(I) pybox carbonyl complexes reveals a correlation between the conformation of the aryl-substituted oxazoline donors and the carbonyl stretching frequency. This correlation is observed in both octahedral rhodium(III) and ruthenium(II) variants and cannot be explained by the classical interpretation of metal-carbonyl bonding. Instead, it is explained by local changes in the electric field projected along the metal-carbonyl vector.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Stanna K. Dorn, Annika E. Tharp, M. Kevin Brown
Summary: The study introduces an efficient, modular, and enantioselective approach towards accessing novel variants of double-allylation reagents via Cu/Pd-catalyzed alkenylation of alkenylboron derivatives. It demonstrates a novel use of allylBdan reagent directly in a stereocontrolled allylation without initial deprotection. These allylation products are utilized in a second intermolecular allylation to access complex diol motifs, signaling the importance and utility of this method in accessing complex structural motifs in a rapid manner.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mengfei Wang, Kei Murata, Yosuke Koike, Gediminas Jonusauskas, Amaury Furet, Dario M. Bassani, Daisuke Saito, Masako Kato, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Kazuyuki Ishii
Summary: A recent study has demonstrated the photo-induced CO-releasing capabilities of the complex Re1Pc, which is composed of a [Re(CO)(3)](+) unit and a phthalocyanine ligand. The complex exhibited efficient spin-orbit coupling and large Franck-Condon factors, resulting in short excited-state lifetimes and ultrafast intersystem crossing. This research provides promising insights into the development of red-light-driven photoCORMs for biomedical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Elena Cuellar, Laura Pastor, Gabriel Garcia-Herbosa, John Nganga, Alfredo M. Angeles-Boza, Alberto Diez-Varga, Tomas Torroba, Jose M. Martin-Alvarez, Daniel Miguel, Fernando Villafane
Summary: New cis-(1,2-azole)-aquo bis(2,2'-bipyridyl)-ruthenium(II) complexes were synthesized and characterized, with photophysical and electrochemical studies revealing their catalytic activity in CO2 reduction. The photocatalytic experiments demonstrated high turnover numbers for CO and formic acid production under specific conditions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Alvaro Garcia-Romero, Jose M. Martin-Alvarez, Daniel Miguel, Dominic S. Wright, Celedonio M. Alvarez, Raul Garcia-Rodriguez
Summary: This study reveals the formation of a common hybrid metal-organic framework structure with Cu(I) and Ag(I) salts using tripodal ligands containing antimony and bismuth. It also demonstrates that the greater Lewis acidity of bismuth compared to antimony can lead to the collapse of the MOF structure. This provides insights into how the electronic effects of the bridgehead atoms in these ligand systems can impact their supramolecular chemistry.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Fernando Carrasco, Wilfredo Hernandez, Oscar Chupayo, Patricia Sheen, Mirko Zimic, Jorge Coronel, Celedonio M. Alvarez, Sergio Ferrero, Sandra Oramas-Royo, Evgenia Spodine, Jesus M. Rodilla, Juan Z. Davalos
Summary: Eight new phenylisoxazole isoniazid derivatives were synthesized and showed moderate antituberculous activity, especially exhibiting potential for use against resistant strains of Mycobacterium tuberculosis.
JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lidia A. Perez-Marquez, Marcelle D. Perretti, Raul Garcia-Rodriguez, Fernando Lahoz, Romen Carrillo
Summary: 3-Nitrotyrosine (NT) is an important biomarker of renal damage, but lacks an appropriate sensing method for clinical diagnosis. This study presents a fluorescent supramolecular sensor that selectively detects NT in human blood serum, providing a sensitive detection limit within physiological concentrations observed in chronic kidney disease.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Analytical
Cecilia Ortega-Zamora, Javier Gonzalez-Salamo, Marcelle D. Perretti, David Santana, Romen Carrillo, Javier Hernandez-Borges
Summary: A chain-shattering polymer (CSP) was proposed and synthesized as a degradable sorbent for microdispersive solid-phase extraction (mu dSPE). The CSP exhibited responsive properties and enhanced noncovalent aromatic interactions with analytes. It was successfully applied for the extraction and determination of plasticizers from environmental water samples. The polymer could be efficiently degraded and recovered, showing its potential as a recyclable sorbent.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Adriana Sacristan-Martin, Daniel Miguel, Hector Barbero, Celedonio M. Alvarez
Summary: This article discusses the use of mimicking natural mechanisms to address control and output modulation of molecular machines. The reversible thiol/disulfide motifs in chemical systems are utilized with nonplanar corannulene moieties capable of recognizing fullerenes. Two redox-based machines have been devised: an ON/OFF switch activated by dimerization and a self-resetting host with an automated backward process that substantially modulates its affinity.
Article
Engineering, Chemical
Maria Anderez-Fernandez, Sergio Ferrero, Joao P. S. Queiroz, Eduardo Perez, Celedonio M. Alvarez, Angel Martin, M. Dolores Bermejo
Summary: This study investigates the hydrothermal reduction of glucose and its by-products for formic acid production. The results show that reaction time and temperature significantly impact the yield of formic acid. Additionally, the reduction pathway occurs through the oxidation of by-products rather than the oxidation of glucose itself.
JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS
(2022)
Article
Chemistry, Organic
Adriana Sacristan-Martin, Daniel Miguel, Alberto Diez-Varga, Hector Barbero, Celedonio M. Alvarez
Summary: This study describes the synthesis of a set of fullerene receptors and their interaction with C60 and C70 using corannulene-based molecular tweezers. The affinity towards fullerenes is mainly contributed by London dispersion forces. However, the sulfur-derived subfamily shows better interaction with fullerenes and can form inclusion complexes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tanausu Santos, Yaiza Perez-Perez, David S. Rivero, Raquel Diana-Rivero, Fernando Garcia-Tellado, David Tejedor, Romen Carrillo
Summary: Dynamic Covalent Chemistry (DCvC) plays an increasingly important role in supramolecular chemistry and materials science. In this study, we demonstrate the dynamic nature of the exchange between phenols and vinyl ethers. The fast exchange at room temperature and under mild conditions has been observed. The equilibrium constants and electronic effects of phenol substituents have been calculated. This novel incorporation into the DCvC toolbox holds great potential and has been successfully applied in the synthesis of a responsive molecular cage.
Article
Chemistry, Inorganic & Nuclear
Murphy Jennings, Elena Cuellar, Ariadna Rojo, Sergio Ferrero, Gabriel Garcia-Herbosa, John Nganga, Alfredo M. Angeles-Boza, Jose M. Martin-Alvarez, Daniel Miguel, Fernando Villafane
Summary: New 1,2-azolylamidino complexes were synthesized and characterized. The compounds showed catalytic activity in CO2 electrocatalytic reduction and photocatalytic CO2 reduction, producing CO and formate.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Marcelle D. Perretti, Yaiza Perez-Perez, Kevin Soler-Carracedo, Endika Martin-Encinas, Concepcion Alonso, Jimena Scoccia, Romen Carrillo
Summary: Dynamic nucleophilic aromatic substitution of tetrazines (S(N)Tz) has been used to build theranostic prodrugs that are activated by hydrogen sulfide, allowing for selective release of drugs and/or fluorescent compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Adriana Sacristan-Martin, Hector Barbero, Sergio Ferrero, Daniel Miguel, Raul Garcia-Rodriguez, Celedonio M. alvarez
Summary: In this study, molecular tweezers for fullerene recognition were developed based on 2,2 '-bipyridine-bearing corannulene motifs, allowing for selective syn or anti confirmation through Cu(i) coordination/decoordination. This control mechanism enables effective metal-triggered ON/OFF molecular tweezers for fullerene recognition.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Alvaro Garcia-Romero, Jose M. Martin-Alvarez, Annie L. Colebatch, Alex J. Plajer, Daniel Miguel, Celedonio M. Alvarez, Raul Garcia-Rodriguez
Summary: The study presents a rare metallic anion [EtAl(3-py)(3)](-) with high protic stability against water and alcohols, unlike related compounds, due to its inability to chelate Li+ and prevent a decomposition pathway involving Li/Al cooperativity.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
