Article
Chemistry, Organic
E. H. Nisala Fernando, Jose Cortes Vazquez, Jacqkis Davis, Weiwei Luo, Vladimir N. Nesterov, Hong Wang
Summary: The formation of enamine from primary arylamines was studied and confirmed, with the necessity of a radical quencher for detection. A direct synthesis of alpha-enaminones from primary arylamines and ketones was developed, and a mechanistic investigation suggested the involvement of an amine radical cation. The reactivity and utility of alpha-enaminones were explored, showing different properties from enamines and advancing understanding in organic chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Miguel Sanchez-Fuente, Alberto Lopez-Magano, Alicia Moya, Ruben Mas-Balleste
Summary: Condensation of BINAPO-(PhCHO)(2) and 1,3,5-tris(4-aminophenyl)benzene(TAPB) leads to a new imine-based chiral organic material (COM) that can be post-functionalized through reductive transformation of imine linkers to amines. Although the imine-based material is not stable enough to be used as a heterogeneous catalyst, the reduced amine-linked framework can be efficiently utilized in asymmetric allylation of various aromatic aldehydes. The obtained yields and enantiomeric excesses are comparable to those observed for the molecular BINAP oxide catalyst, with the added advantage of recyclability offered by the amine-based material.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Organic
Isaac G. Sonsona, Andrea Vicenzi, Marco Guidotti, Giorgiana Denisa Bisag, Mariafrancesca Fochi, Raquel P. Herrera, Luca Bernardi
Summary: The study demonstrates the improved selectivity of an asymmetric aldol reaction by replacing part of the catalyst, and identifies the most suitable reaction conditions. However, these conditions seem to be limited to oxindoles bearing a 3-substituent of funapide.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Ciril Jimeno
Summary: The research was inspired by the binding and stabilizing effect of arginine residues in certain aldolases, leading to the development of a new family of amino acylguanidine organocatalysts. Screening and optimization identified the threonine derivative as the most suitable catalyst for asymmetric aldol addition, while the proline derivative yielded the anti diastereomer. MMFF models indicated the presence of an extensive hydrogen bonding network between the acylguanidinium group and the reaction intermediates.
Article
Chemistry, Physical
Pratikkumar Lakhani, Chetan K. Modi
Summary: In this work, a groundbreaking strategy for the synthesis of L-proline chiral scaffold tethered onto the silica matrix was reported. The synthesized catalyst showed excellent activity in an asymmetric aldol reaction with high enantioselectivity. Moreover, the catalyst could be recycled multiple times without any loss of activity.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Wei Xiao, Zihao Wang, Jinxiang Yang, Meishuang Qiu, Yan Peng, Xiaorong Xiong, Yizhuo Lu, Tianyou Chen, Zushun Xu
Summary: Colloidal polystyrene-supported cooperative imidazolidinone/thiourea catalysts were developed for efficient aldol reaction and substrate-selective Knoevenagel condensation in water, with the synergistic effect of hydrophobic interaction and hydrogen bonding between the substrates and catalysts playing a crucial role. These catalysts show great potential for efficient and selective catalysis in other reactions.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Veronica Diaz-Juarez, Carlos Ernesto Reyes-Escobedo, Mario Perez-Venegas, Eusebio Juaristi, Salvador Perez-Estrada, Susana Rojas-Lima, Heraclio Lopez-Ruiz
Summary: The (S)-proline-thiourea 1 host-guest complex is reported as an efficient catalyst in the enantioselective aldol reaction of ketones with aldehydes. This complex shows high yields, enantioselectivities, and diastereoselectivities under various conditions, such as at 0 degrees C, in a non-polar solvent like toluene, or under solvent-less conditions.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Stuart C. D. Kennington, Saul F. Teloxa, Miguel Mellado-Hidalgo, Oriol Galeote, Sabrina Puddu, Marina Bellido, Pedro Romea, Felix Urpi, Gabriel Aullon, Merce Font-Bardia
Summary: A direct and asymmetric aldol reaction of N-acyl thiazinanethiones with aromatic aldehydes catalyzed by chiral nickel(II) complexes was reported. The reaction gives high yields of O-TIPS-protected anti-aldol adducts with remarkable stereocontrol and atom economy. The removal of the achiral scaffold provides enantiomerically pure intermediates with synthetic interest for producing anti-alpha-amino-beta-hydroxy and alpha,beta-dihydroxy carboxylic derivatives, with theoretical calculations explaining the observed high stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Axel Leblond, Ines Houari, Yann Beauxis, Karine Leblanc, Erwan Poupon, Mehdi A. Beniddir
Summary: In this study, an unconventional strategy was used to mimic the catalytic conditions of ketosterase, leading to the successful synthesis of nesteretal A and its analogues.
Article
Chemistry, Multidisciplinary
Bo-Bo Gou, Yue Tang, Yan-Hong Lin, Le Yu, Qing-Song Jian, Huai-Ri Sun, Jie Chen, Ling Zhou
Summary: A new type of chiral all-carbon tetrasubstituted VQMs was successfully prepared via nucleophilic addition of 2-alkynylnaphthols to o-quinone methides or imines, catalyzed by chiral phosphoric acids. The method showed high efficiency and excellent diastereoselectivities and enantioselectivities, leading to the synthesis of naphthyl-2H-chromenes with axially and centrally chiral elements and axially chiral quinone-naphthols. The obtained axially chiral naphthols could further be converted into valuable phosphine ligands and other functional molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Aolin Cheng, Liangliang Zhang, Qinghai Zhou, Tao Liu, Jing Cao, Guoqing Zhao, Kun Zhang, Guanshui Song, Baoguo Zhao
Summary: The direct asymmetric aldol reaction of glycinates has been achieved by using chiral N-methyl pyridoxal as the catalyst, leading to high yields of chiral beta-trifluoromethyl-beta-hydroxy-alpha-amino-acid esters with excellent stereoselectivity and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ningning Zhang, Zhiyong Sun, Changzhu Wu
Summary: The polymeric approach of combining proteins with organocatalytic polymers to generate artificial enzymes expands the applications of asymmetric organocatalysis and provides new avenues for combining proteins/enzymes with well-designed organocatalytic polymers for useful synthetic reactions.
Article
Chemistry, Applied
Maxim Smirnov, Alexander S. Kucherenko, Ilya D. Gridnev, Alexander A. Korlyukov, Sergei G. Zlotin
Summary: Biomass derived gamma-pyrone-2-carbaldehydes were used as a robust platform for carrying out organocatalytic asymmetric cross-aldol reactions with high yield and excellent stereoinduction. The origins of efficient stereoinduction were revealed by quantum-chemical calculations, and the products were successfully converted to synthetically useful chiral compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Kazumasa Kon, Hiromu Takai, Takumu Kobayashi, Yoshihito Kohari, Miki Murata
Summary: An organocatalyzed asymmetric aldol reaction of α-keto amides has been developed, with an N-terminal 4-trans-siloxyproline-based tripeptide as the catalyst, yielding aldol adducts with up to 99% yield and 91% ee.
Article
Chemistry, Organic
David Guzman Rios, Miguel A. Romero, Jose A. Gonzalez-Delgado, Jesus F. Arteaga, Uwe Pischel
Summary: The [Ru(bpy)2(Nor)2]2+ complex is an efficient catalyst for the aldol reaction of acetone with activated benzaldehydes in a buffered aqueous solution. The role of the metal as an activator for nornicotine organocatalyst ligands enhances catalytic activity by about 4.5 times compared to free nornicotine. The study provides insights into the synergistic effect of organic catalysts and metals.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Johannes E. Erchinger, Manuel van Gemmeren
Summary: This article discusses the combination of electrochemistry and Pd-catalyzed C-H activation/functionalization to achieve C-C, C-X, C-O, and C-P bond formation.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Arup Mondal, Manuel van Gemmeren
Summary: Alkynes are important motifs in organic synthesis due to their presence in natural products and bioactive molecules. The method of inserting alkynes into (hetero)arenes relies heavily on the regioselectivity of the halogenation step, and can achieve selective alkynylation of thiophenes. The developed palladium-catalyzed C-H activation/alkynylation of thiophenes allows for regiodivergent reactions and late-stage modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Editorial Material
Chemistry, Multidisciplinary
Sabine Bognar, Manuel van Gemmeren
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Editorial Material
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Alberto Martinez-Cuezva, Jose Berna
Summary: The researchers demonstrate how the ring motion of the [2]rotaxane-based linker and the surrounding triphenylene-based struts influence each other within a series of robust zirconium(IV) organic frameworks in the latest issue of Chem.
Article
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Aurelia Pastor, Alberto Martinez-Cuezva, Jose Berna
Summary: Self-templating two-component coupling reactions resulted in the isolation of two threaded products with different molecular sizes: a lasso-type rotaxane and a daisy chain rotaxane. Their distribution in the final reaction mixture varies depending on the concentration of the reactants. This methodology also allowed the synthesis of a large 84-membered cyclic multistation rotaxane.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Teresa Paez, Alberto Martinez-Cuezva, Rebeca Marcilla, Jesus Palma, Edgar Ventosa
Summary: Aqueous organic redox flow batteries (AORFBs) have been gaining attention as a sustainable solution for stationary energy storage. However, they still face challenges, particularly in terms of capacity fading upon cycling. This study proposes a simple electrochemical balancing procedure to mitigate capacity fading and prolong cycling performance, showing promising results in two case studies.
JOURNAL OF POWER SOURCES
(2021)
Article
Chemistry, Multidisciplinary
Carmen Lopez-Leonardo, Adrian Saura-Sanmartin, Marta Marin-Luna, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: This study describes the synthesis of chiral mechanically interlocked molecules and explores their applications in catalysis and sensing. The results demonstrate that enantioenriched value-added compounds can be obtained through base-promoted cyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jesus de Maria Perez, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: The study found that glutaconamide-based [2]rotaxanes can be efficiently oxidized to interlocked alpha-ketoamides, while their non-interlocked threads produce hydroxycyclohexene tetraamides under similar reaction conditions. These results demonstrate the powerful control of chemical behavior by mechanically interlocking highly reactive substrates. Under light irradiation inside the macrocycle, the alpha-ketoamide threads undergo divergent intramolecular cyclizations to form interlocked hydroxy-beta-lactams or oxazolidinones, processes that are efficiently chemocontrolled by the mechanical bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tainara Orlando, Jesus de Maria Perez, Fellipe Freire Santos Farias, Paulo Roberto dos Santos Salbego, Alberto Martinez-Cuezva, Marcos Antonio Pinto Martins, Jose Berna
Summary: Understanding the nature of the mechanical bond is crucial for the design of new mechanically interlocked molecules. This study investigated the formation of different crystalline phases by examining the freedom degree of interlocked components in rotaxanes. Through crystallization experiments and various solvents, 15 crystalline phases were obtained for five studied compounds. The intercomponent interactions were evaluated in solution and the solid state, and it was found that all rotaxanes had the same type of interaction, although the distribution of interaction energies varied depending on the crystalline phase.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Tomas Nicolas-Garcia, Aurelia Pastor, David Quinonero, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: This paper reports the synthesis of a ditopic interlocked building-block and its self-assembly into a cyclic dimer. NMR studies identified a cyclic hetero[4]pseudorotaxane as the main supramolecular structure in solution. Computational studies revealed that the assembly is the result of positive cooperativity in the hydrogen-bonding-driven assembly of this mechanically interlocked supramolecule. The disassembly of the cyclic dimer was achieved through a Diels-Alder reaction and competitive molecular recognition.
Review
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Aurelia Pastor, Alberto Martinez-Cuezva, Guillermo Cutillas-Font, Mateo Alajarin, Jose Berna
Summary: This review focuses on the chemistry of incorporating mechanical bonds into metal-organic frameworks (MOFs). The article first introduces the fundamental concepts of mechanically interlocked molecules (MIMs) and MOFs, then summarizes the advances in incorporating rotaxanes and catenanes into MOF matrices. The review concludes by discussing the dynamics of rotaxanes in MOFs and the operation of stimulus-responsive MIMs in MOFs, offering a critical opinion on the current state of the research field and suggesting key areas for future focus.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Jesus de Maria Perez, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: The catalytic activity of degenerate succinamide-based [2]rotaxanes can be modulated by changes at their macrocyclic component. The variation in catalytic efficiency is correlated with the electronics and dynamics of the entwined macrocycle.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Carlos Santiago, Hao Chen, Arup Mondal, Manuel van Gemmeren
Summary: In this study, dual ligand-based palladium catalysts were used for late-stage olefination of arenes, successfully functionalizing complex arene substrates. The method utilizes the arene as a limiting reactant and controls the regioselectivity of the transformation by the steric and electronic properties of the substrate, providing a new pathway for preparing regioisomers.
Article
Chemistry, Multidisciplinary
Alberto Martinez-Cuezva, Aurelia Pastor, Marta Marin-Luna, Carmen Diaz-Marin, Delia Bautista, Mateo Alajarin, Jose Berna
Summary: This study investigates the CsOH-promoted diastereoselective cyclization of interlocked fumaramides to form beta-lactams. Experimental evaluation, KIE studies, and computational analysis indicate that the rate-determining step involves deprotonation of the N-benzyl group by the amidate group from the macrocycle. The polyamide macrocycle plays a crucial role in both activation and diastereoselection. Additionally, increased flexibility of the adamantyl core accelerates the cyclization process in diadamantyl-derived rotaxanes.
Article
Chemistry, Organic
Manuel van Gemmeren, Benjamin List
Summary: This article details the development of Select Crowd Reviewing from the initial idea through a pilot phase to its current status as the default method for evaluating manuscripts at Synlett and SynOpen. The workflow for manuscript evaluation using Select Crowd Reviewing is described, along with a discussion of the advantages it offers compared to traditional peer review.
