Review
Chemistry, Multidisciplinary
Chongqing Pan, Zhenhua Gu
Summary: Atropisomerism is a prominent stereochemical behavior arising from restricted rotation, and it has been widely applied in bioactive substances, catalysts, and materials science. Transition-metal-catalyzed asymmetric carbene transformation reactions provide an effective strategy to achieve extraordinary stereocontrol in atropisomers.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tian-Ci Wang, Ling Zhu, Shiwei Luo, Zhong-Sheng Nong, Pu-Sheng Wang, Liu-Zhu Gong
Summary: Asymmetric functionalization of the C(sp(3))-H bond using chiral phosphoramidite-palladium catalysis was successfully achieved in this study, leading to the synthesis of enantioenriched beta-amino-gamma,delta-unsaturated carbonyl derivatives and providing a key intermediate for the asymmetric synthesis of Focalin. The research also revealed an umpolung reactivity of N-allylimines through a concerted proton and two-electron transfer process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Kaiting Zheng, Yaomei Liu, Chenggong Zheng, Fangpei Yan, Hua Xiao, Yi-Si Feng, Shilu Fan
Summary: A palladium-catalyzed monofluoroalkylation method using nucleophilic ethyl 2-fluoro-2-(trimethylsilyl)acetate as a monofluoroalkyl source was developed. The reaction exhibited excellent substrate scope, providing a range of monofluoroalkylated products in good yields under mild conditions. This protocol was successfully applied in the late-stage modification of an estrone derivative, offering a facile route for the discovery of biologically active compounds and high-performance materials.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Sven Kirschner, Matthew Peters, Kang Yuan, Marina Uzelac, Michael J. Ingleson
Summary: This study demonstrates for the first time that organoboranes with high fluorophilicity, such as BEt3 and 3,5-(CF3)(2)C6H3-BPin, can serve as effective solid to solution phase-transfer catalysts for the fluorination of certain organohalides with CsF. Chiral induction during nucleophilic fluorination can also be achieved using oxazaborolidine (pre)catalysts and CsF. The fluoride affinity of the borane and the ligation of Cs+ play important roles in the fluorination process.
Article
Chemistry, Organic
Li-Wen Sun, Ya-Fei Hu, Wen-Jun Ji, Peng-Yuan Zhang, Mengtao Ma, Zhi-Liang Shen, Xue-Qiang Chu
Summary: The auxiliary function of a carbonyl group in the tunable defluorophosphination and defluorophosphorylation of trifluoromethylated enones with P(O)-containing compounds was demonstrated. Controlled replacement of one or two fluorine atoms in trifluoromethylated enones while maintaining high chemo- and stereoselectivity was achieved under mild conditions, thus enabling diversity-oriented synthesis of skeletally diverse organophosphorus libraries-(Z)-difluoro-1,3-dien-1-yl phosphinates, (1Z,3E)-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl phosphinates, and (E)-4-phosphoryl-4-fluoro-1,3-but-3-en-1-ones-in good yields with excellent functional group tolerance.
Article
Chemistry, Physical
Yaxiong Tian, Ningning Liu, Jiali Li, Tunmise Ayode Otitoju, Ting Sun, Huichun Xue
Summary: In this study, F and N co-doped porous carbon (FNC) derived from covalent organic frameworks (COFs) was synthesized and utilized as an anode for potassium-ion batteries (PIBs) for the first time. FNC retains COFs characteristics, including a nanosheet structure, hierarchical pores, and large interlayer spacing, facilitating potassium ion diffusion and providing active sites for storage. Introduction of F and N by COFs molecules enables the formation of conjugation effect, stable C-F bonds, and -C-F...N-interactions, improving the electrical conductivity and structural stability of FNC. As a result, the FNC anode exhibits high reversible specific capacity of 292 mAh g-1 at 50 mA g-1 and excellent cyclability of 118 mAh g-1 at 1000 mA g-1 over 200 cycles.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Chemistry, Multidisciplinary
Julia Krueger, Christoph Woelper, Stephan Schulz
Summary: The reactivity study showed the nucleophilic character of the pnictogen and the electrophilic nature of the Ga atom in LGaEGa(Cl)L. Depending on the reaction conditions, different compounds can be synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Samantha A. Orr, Philip C. Andrews, Victoria L. Blair
Summary: Main-group-metal-mediated transformations of imines play a significant role in synthetic chemistry by allowing the simple preparation of various nitrogen-containing compounds. Recent advances in imine C-F activation protocols and catalytic methods for hydroelementation highlight the importance of imines in sustainable chemistry. The incorporation of imines into flow chemistry has also received attention as a noteworthy development.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Meizhong Tang, Ye-Xin Wang, Shenlin Huang, Lan-Gui Xie
Summary: This article reports a method for the selective synthesis of α-sulfenylated α,β-unsaturated aldehydes from terminal alkynes using a suitable oxidant. The mild conditions of this method enable the conversion of a wide range of terminal alkynes, bearing various functionalities or derived from drug and bioactive molecules, to their α,β-unsaturated aldehyde analogues with excellent chemo-, regio-, and stereoselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Yajun Li, Hongli Bao
Summary: This article discusses recent advances in the synthesis of allenes via radical intermediates, categorizing them into different types of substrates and distinct catalytic systems. Mechanistic studies and synthetic challenges are highlighted.
Article
Chemistry, Multidisciplinary
Martin Tomanik, Jin-Quan Yu
Summary: This article reports a palladium-catalyzed annulation reaction that synthesizes a variety of five-membered benzo-fused compounds through sequential reactions of methyl positions and aryl positions. By using a dual-ligand system, this reaction is promoted and the products are obtained effectively.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Zhenghui Wen, Diego Pintossi, Manuel Nuno, Timothy Noel
Summary: This study presents organic solvent nanofiltration (OSN) as a solution to reduce TBADT consumption and increase its turnover number, enabling large-scale photocatalytic transformations. With in-line TBADT recovery, the observed product yields are comparable to those of reactions performed with pristine TBADT.
NATURE COMMUNICATIONS
(2022)
Article
Engineering, Environmental
Jie Xu, Xin Zhang, Jing Long, Chang Ge
Summary: Photocatalysis is considered a promising method for obtaining aromatic compounds under mild reaction conditions, but the development of heterogeneous photocatalysts with high catalytic activity still faces many challenges. This study successfully developed a new photocatalytic strategy, using nitrogen-doped graphitic carbon nitride, potassium persulfate, and water, to efficiently break the C-C bonds in lignin under mild conditions.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Jia-Lin Tu, Ao-Men Hu, Lin Guo, Wujiong Xia
Summary: In this study, undirected iron-catalyzed C(sp3)-H borylation, thiolation, and sulfinylation reactions were developed using the photoinduced ligand-to-metal charge transfer (LMCT) process. These reactions showed broad substrate scope and unconventional regioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Subhankar Pradhan, Priyanka Chakraborty, Soumen Paira, Basker Sundararaju
Summary: Allenyl carbonate was used as a 1,3-butadiene surrogate to develop a photocatalytically sustainable protocol for cobalt-catalyzed crotylation of aldehydes. The developed method tolerated a wide range of aromatic and aliphatic aldehydes with retention of functional groups under mild conditions and produced good-to-excellent yields of crotylated secondary alcohols. A plausible mechanism is proposed based on preliminary mechanistic studies and literature precedents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guillermo Marcos-Ayuso, Agusti Lledos, Juan A. Casares
Summary: Experimental studies and calculations show that the oxidative addition of aryl halides to copper complexes follows different paths depending on the nature of the halogen. For bromine, a concerted addition leads to the formation of a C-C coupled product, while for iodine, a different complex is formed and an elimination reaction occurs.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jose-Emilio Sanchez-Aparicio, Giuseppe Sciortino, Eric Mates-Torres, Agusti Lledos, Jean-Didier Marechal
Summary: This study explores the challenges and solutions in molecular modelling applications in metalloenzyme design. By incorporating new tools in multiscale strategies, particularly substrate diffusion exploration, a deeper understanding of metal-mediated binding and catalytic geometry can be achieved. Using various variants of an artificial Rh-2-based cyclopropanase as examples, DFT calculations and molecular dockings reveal the catalytic mechanisms controlled by the protein.
FARADAY DISCUSSIONS
(2022)
Article
Chemistry, Applied
Gantulga Norjmaa, Gregori Ujaque, Agusti Lledos
Summary: The use of solvent effects in computational modeling of homogeneous catalysis is essential for capturing accurate mechanistic details. While continuum solvent models are commonly used, explicit solvent models are often necessary to provide a more detailed and accurate representation, leading to improved mechanistic understanding of reactions. Through selected examples, this article highlights the limitations of continuum solvent models and the benefits of incorporating explicit solvent molecules in quantum mechanical descriptions.
TOPICS IN CATALYSIS
(2022)
Article
Green & Sustainable Science & Technology
Alberto Lopez-Magano, Ruben Mas-Balleste, Jose Aleman
Summary: The study demonstrated the stable coordination of palladium centers by the phenanthroline unit in Phen-COF, leading to enhanced catalytic activities and recyclability. The concept of isolating and immobilizing catalytic sites in Pd@Phen-COF significantly improved catalytic outputs compared to analogous molecular catalysts, particularly in C-C cross-coupling reactions.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Correction
Chemistry, Physical
Fadri Christoffel, Nico V. Igareta, Michela M. Pellizzoni, Laura Tiessler-Sala, Boris Lozhkin, Daniel C. Spiess, Agusti Lledos, Jean-Didier Marechal, Ryan L. Peterson, Thomas R. Ward
Article
Chemistry, Inorganic & Nuclear
Elena Borrego, Laura Tiessler-Sala, Jesus J. Lazaro, Ana Caballero, Pedro J. Perez, Agusti Lledos
Summary: The direct oxidation of benzene into phenol using a copper complex catalyst is investigated. The dinuclear species Tp(Br3)Cu(II)(mu-O-center dot)(mu-OH)Cu(II)Tp(Br3) is proposed as the key structure responsible for activating the arene C-H bond leading to phenol formation.
Article
Chemistry, Inorganic & Nuclear
Laura Tiessler-Sala, Giuseppe Sciortino, Lur Alonso-Cotchico, Laura Masgrau, Agusti Lledos, Jean-Didier Marechal
Summary: In this study, computational techniques were used to investigate and compare the mechanisms of two heme-binding systems. The results revealed different heme-binding mechanisms between the two systems, with one system having similar conformational spaces in the absence and presence of heme, while the other system only exhibited similar conformations to the holo form when heme was bound. This study highlights the diversity of molecular mechanisms of heme-binding.
INORGANIC CHEMISTRY
(2022)
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, Physical
Sarah E. Jenny, Juan M. Serviano, Ainara Nova, Graham E. Dobereiner
Summary: This study proposes a reaction pathway for a precatalyst that exhibits high Z selectivity in alkene isomerization. Computational modeling suggests that the isomerization occurs through an allyl hydride shift mechanism, where hydride migration from one position to another takes place. This is the first study to propose such a hydride migration mechanism in alkene isomerization.
Article
Chemistry, Physical
Linn Neerbye Berntsen, Ainara Nova
Summary: We studied the mechanism of selective Cu-catalyzed N-arylation of hydantoins using unsymmetrical aryl(TMP)iodonium salts and found that deprotonation of hydantoin precedes the oxidative addition of the aryl(TMP)iodonium salt. The rate-limiting steps are the oxidative addition to a Cu(I) imido intermediate and ligand rearrangements. Our findings are consistent with experimental observations and provide insights for enhancing the efficiency of arylation reactions by tuning the diaryliodonium salt.
Article
Chemistry, Physical
Yunfei Bai, Esben Taarning, Mahika Luthra, Lars F. Lundegaard, Anna Katerinopoulou, Hanne Falsig, Ainara Nova, Juan S. Martinez-Espin
Summary: The crystal structure of Sn-Beta materials was investigated using PXRD, and a strong correlation between lattice parameters and the concentration of tin and defects was observed. PT Sn-Beta samples with more defects showed extended interlayer distance and expansion of translation symmetry, resulting in larger unit cell dimensions. In contrast, HT Sn-Beta samples with fewer defects showed minimal effect of tin site density on unit cell volume.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Review
Chemistry, Physical
Miguel Sanchez-Fuente, Jose Lorenzo Alonso-Gomez, Laura M. Salonen, Ruben Mas-Balleste, Alicia Moya
Summary: This review provides an overview of the development of chiral porous organic frameworks as candidates for heterogeneous asymmetric organocatalysis. The synthetic strategies, characterization techniques, and applications of chiral organic materials in asymmetric organocatalysis are summarized. Various types of porous organic frameworks are described, and strategies for incorporating chirality in these materials are presented. The review focuses on the applications of chiral porous organic frameworks in asymmetric organocatalytic reactions, summarizing and categorizing the available literature in the field.
Article
Chemistry, Multidisciplinary
Ashleigh M. Chester, Celia Castillo-Blas, Roman Sajzew, Bruno P. Rodrigues, Ruben Mas-Balleste, Alicia Moya, Jessica E. Snelson, Sean M. Collins, Adam F. Sapnik, Georgina P. Robertson, Daniel J. M. Irving, Lothar Wondraczek, David A. Keen, Thomas D. Bennett
Summary: This study explores the characterization of hybrid blends comprising a metal-organic framework (MOF) glass and a phosphate glass. The mechanical and thermal properties of the blends are studied, and the interfacial interactions between the phases are analyzed.
Article
Chemistry, Multidisciplinary
Ashleigh M. Chester, Celia Castillo-Blas, Roman Sajzew, Bruno P. Rodrigues, Ruben Mas-Balleste, Alicia Moya, Jessica E. Snelson, Sean M. Collins, Adam F. Sapnik, Georgina P. Robertson, Daniel J. M. Irving, Lothar Wondraczek, David A. Keen, Thomas D. Bennett
Summary: This study explores the characterization of hybrid blends comprising a metal-organic framework (MOF) glass and a phosphate glass. The mechanical and thermal properties of the blends are studied, and the interfacial interactions between the phases are analyzed.
Review
Chemistry, Multidisciplinary
Saba Daliran, Ali Reza Oveisi, Yong Peng, Alberto Lopez-Magano, Mostafa Khajeh, Ruben Mas-Balleste, Jose Aleman, Rafael Luque, Hermenegildo Garcia
Summary: C-H functionalization, although simple, requires highly active and selective catalysts. Recent research has focused on using porous materials such as MOFs, COFs, and POPs as heterogeneous catalysts, due to their promising activity and tunability. These materials offer structural uniformity, easy tunability, and permanent porosity, and their catalytic selectivity can be controlled through engineering their microenvironments.
CHEMICAL SOCIETY REVIEWS
(2022)