Article
Chemistry, Organic
Xinmiao Huang, Ling Tang, Zhiyong Song, Shuangshuang Jiang, Xianmao Liu, Ming Ma, Bo Chen, Yuanhong Ma
Summary: A nickel catalysis system has been developed for the desulfonylative C(sp(2))-C(sp(2)) reductive cross-coupling reactions of aryl sulfone derivatives with aryl bromides to form diverse biaryl compounds. The isolated and confirmed Ar-Ni(II)-SO(2)CF3 complex with a phosphine ligand through oxidative addition of aryl sulfone to Ni(0) species provides solid evidence for understanding the C(Ar)-SO2 bond activation and reaction mechanism.
Article
Chemistry, Multidisciplinary
Aleksandra Potrzasaj, Mateusz Musiejuk, Wojciech Chaladaj, Maciej Giedyk, Dorota Gryko
Summary: This study presents a method for the selective synthesis of linear products from epoxides using a vitamin B-12/Ni dual-catalytic system. This method complements approaches that provide branched alcohols and relies on blue-light irradiation for the reaction to occur. Both experimental and theoretical studies support the proposed mechanism involving alkylcobalamin as an intermediate in this process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Haoyu Li, Xinxin Tang, Jia Hao Pang, Xiangyang Wu, Edwin K. L. Yeow, Jie Wu, Shunsuke Chiba
Summary: This study reveals the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. By photoexcitation of tetrasulfide dianions, single-electron reduction of aryl halides is achieved, leading to the participation of aryl radicals in cross-coupling, borylation, and hydrogenation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Fusheng Bie, Xuejing Liu, Han Cao, Yijun Shi, Tongliang Zhou, Michal Szostak, Chengwei Liu
Summary: The Pd-catalyzed double-decarbonylative synthesis of aryl thioethers involves an aryl exchange reaction between amides and thioesters, with amides serving as aryl donors and thioesters as sulfide donors. The use of Pd/Xantphos without any additives promotes aryl exchange by C(O)-N/C(O)-S cleavages, allowing for a wide variety of amides and sulfides to be used in the reaction.
Article
Chemistry, Applied
Ruizhe Wang, Xinyu Wang, Shuai Mao, Yahao Zhao, Bo Yuan, Xue-Yan Yang, Jianjun Li, Zhengkai Chen
Summary: A light-mediated C-Se bond coupling reaction between aryl halides and diselenides has been achieved under mild and photocatalyst-free conditions, resulting in the synthesis of aryl selenoethers. The transformation offers readily available materials, mild reaction conditions, a broad substrate scope, and high efficiency. A plausible mechanism has been proposed based on the initial mechanistic investigation, and the protocol is also applicable for forging C-S and C-Te bonds using disulfides and ditellurides.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ryota Isshiki, Miki B. Kurosawa, Kei Muto, Junichiro Yamaguchi
Summary: A Ni-catalyzed aryl sulfide synthesis method was developed using 2-pyridyl sulfide as the sulfide donor, eliminating the need for odorous and toxic thiols. The Ni/dcypt catalyst played a crucial role in the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, with mechanistic studies showing its ability to undergo oxidative additions and ligand exchanges simultaneously.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Xin Wang, Yueyue Ma, Jinxing Ye, Zhen Liu, Ruihua Cheng
Summary: Based on our previous experimental studies, a broad substrate scope has been developed under mild conditions in the reductive neutral cross-coupling reaction of aryl bromides and arylamines using different nickel catalysts and ligands. The catalytic activity is greatly affected by the substituents on the bipyridine or tridentate ligands. Although the mechanism is still unclear, the formation of carbon radicals and the regeneration of low-valent nickel species under electrolysis have been experimentally proposed. In this work, a theoretical electrochemical study using DFT calculations was conducted to explore the electrochemical neutral cross-coupling reaction.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Giuseppe Dilauro, Francesco Messa, Fabio Bona, Serena Perrone, Antonio Salomone
Summary: A simple cobalt complex, Co(phen)Cl₂, has been found to be a highly efficient and cost-effective precatalyst for various cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl, and alkyl bromides. New C(sp²)-C(sp²) and C(sp²)-C(sp³) bonds can be formed in good to excellent yields and high chemoselectivity under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Kartic Manna, Ranjan Jana
Summary: We describe a mild and highly selective palladium-catalyzed cross-electrophile coupling between aromatic diazonium salts and aryl iodides or diaryliodonium salts in a water-ethanol (2:1) medium. Mechanistic studies revealed the importance of ethanol in generating an active Pd(0) catalyst, and the counterion of the diazonium salt promotes the formation of a cationic Pd(II) species that facilitates subsequent oxidative addition to aryl iodides/diaryliodonium salts. The presence of silver(I) salt is crucial for maintaining the catalytic activity of palladium by removing iodide ions as precipitates.
Article
Chemistry, Organic
Tatsushi Yabuta, Masahiko Hayashi, Ryosuke Matsubara
Summary: The article reports a visible-light-induced photocatalytic cleavage method for alkyl aryl ether C-O bonds using a carbazole-based organic photocatalyst. Addition of Cs2CO3 is beneficial for the reaction, especially in reactions using a N-H carbazole organic photocatalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jinhui Xu, Jilei Cao, Xiangyang Wu, Han Wang, Xiaona Yang, Xinxin Tang, Ren Wei Toh, Rong Zhou, Edwin K. L. Yeow, Jie Wu
Summary: This article discusses the unprecedented discovery that a family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts can activate reductively recalcitrant aryl chlorides under mild conditions, producing valuable organic synthesis products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Lars J. Wesenberg, Alessandra Sivo, Gianvito Vile, Timothy Noel
Summary: In recent years, there has been a trend in the synthetic community to introduce sp(3)-carbon-based fragments in organic compounds through cross-coupling strategies. This study presents a novel nickel-catalyzed electrochemical methodology for reductive cross-electrophile coupling, using inexpensive amine-derived radical precursors and aryl iodides. The use of electrochemistry as a power source reduces waste and avoids chemical reductants, making this approach a more sustainable alternative to traditional cross-coupling methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuli He, Marino Borjesson, Huayue Song, Yuhang Xue, Daning Zeng, Ruben Martin, Shaolin Zhu
Summary: A new catalytic blueprint was reported in this study, merging the modularity of nickel catalysis for bond formation with the ability to enable a rather elusive 1,4-hydride shift at arene sp(2) C-H sites, thus allowing access to ipso/ortho-difunctionalized arenes from readily available aryl halides under mild conditions and exquisite selectivity profile.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Jie Wang, Qing -Yang Li, Shan -Shan Wang, Xin-Yan Wu, Xingguang Li, Pei-Nian Liu
Summary: We have reported a novel rhodium-catalyzed rearrangement reaction involving N-substituted 2-thiopyridones and diazoesters. This reaction proceeds through the rhodium-catalyzed formation of sulfur ylides, followed by a direct C-N bond cleavage, achieving N-to-C 1,4-pyridyl migration. The protocol can be used to synthesize various thiopyridines with tetrasubstituted carbon stereocenters in moderate to excellent yields, expanding the transformation pattern of sulfur ylide intermediates in rearrangement reactions.
Article
Chemistry, Physical
Daniel Schwalbe-Koda, Omar A. Santiago-Reyes, Avelino Corma, Yuriy Roman-Leshkov, Manuel Moliner, Rafael Gomez-Bombarelli
Summary: In this study, templates for over 100 zeolites were proposed using shape and binding metrics, and dual-OSDA approaches were rationalized. Selectivity maps based on phase competition metrics showed that small- and medium-pore zeolites exhibit stronger shape selectivity towards their templates compared to large-pore zeolites. Shape and volume descriptors were used to identify OSDAs that can act as synergistic pore-fillers for different cavities of zeolites. The application of this theory was demonstrated for the KFI zeolite, where tetraethylammonium and OSDAs repurposed from high-silica LTA synthesis were used as dual OSDAs. This work has the potential to contribute to the discovery of new synthesis routes for known zeolites using shape descriptors and repurposed OSDAs.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Applied
Cristina Martinez, Alejandro Vidal-Moya, Bilge Yilmaz, C. P. Kelkar, Avelino Corma
Summary: Fluidized Catalytic cracking (FCC) is a main conversion process in refineries, using Y zeolite as the main source of activity and selectivity. A new Y zeolite catalyst, Phinesse(TM), based on partial substitution of RE by P, has been developed and shown to have similar performance to the conventional RE stabilized counterpart. The hydrothermal stability of different USYs with different dealumination degrees, containing P or La alone or a combination of both stabilizing elements, was compared. The results provide insights into the benefits of P-La stabilization observed in the commercial PhinesseTM catalyst.
Review
Chemistry, Multidisciplinary
Lichen Liu, Avelino Corma
Summary: This review discusses the structure, synthesis, and catalytic applications of heterogeneous bimetallic catalysts, including binuclear sites, nanoclusters, and nanoparticles. Recent progress in the field of bimetallic catalysts is highlighted, along with the future research directions and prospects in both fundamental and practical aspects of heterogeneous catalysis.
Article
Multidisciplinary Sciences
Pau Ferri, Chengeng Li, Daniel Schwalbe-Koda, Mingrou Xie, Manuel Moliner, Rafael Gomez-Bombarelli, Mercedes Boronat, Avelino Corma
Summary: Approaching the level of molecular recognition of enzymes with solid catalysts is a challenging goal, achieved in this work for the competing transalkylation and disproportionation of diethylbenzene catalyzed by acid zeolites. The key diaryl intermediates for the two competing reactions only differ in the number of ethyl substituents in the aromatic rings, and therefore finding a selective zeolite able to recognize this subtle difference requires an accurate balance of the stabilization of reaction intermediates and transition states inside the zeolite microporous voids.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Risheng Bai, Guangyuan He, Lin Li, Tianjun Zhang, Junyan Li, Xingxing Wang, Xiumei Wang, Yongcun Zou, Donghai Mei, Avelino Corma, Jihong Yu
Summary: In this work, a carbonization-reduction method was used to create palladium carbide subnanometric species within pure silicate MFI zeolite. The developed catalyst showed superior performance in the selective hydrogenation of alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Francisco Gonell, Miriam Rodenes, Santiago Martin, Mercedes Boronat, Ivan Sorribes, Avelino Corma
Summary: Developing precious-metal-free electrocatalysts for the hydrogen evolution reaction (HER) is crucial. Amorphous molybdenum sulfide-based materials provide highly active HER electrocatalysts by introducing active sites at both the edge positions and the typically inactive basal planes. The bottom-up synthesis using molecular complexes with Mo3S4 and Mo3S7 cluster cores enhances the HER activity and allows the modification of the derived materials with atomic-scale precision.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Miriam Rodenes, Frederic Dhaeyere, Santiago Martin, Patricia Concepcion, Avelino Corma, Ivan Sorribes
Summary: A defect-engineered molybdenum sulfide catalyst is used to establish straightforward synthetic processes using alcohols. Developing tandem catalytic strategies based on readily available, stable, and renewable feedstocks is crucial for sustainable chemical industries. The catalyst, defect-engineered basal planes of a molybdenum sulfide nanomaterial ({Mo3S4}( n )), enables one-pot single-step synthesis and facilitates various coupling reactions involving alcohol dehydrogenation and hydrogen activation processes.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Reisel Millan, Estefania Bello-Jurado, Manuel Moliner, Mercedes Boronat, Rafael Gomez-Bombarelli
Summary: This study reports a machine learning method to accurately simulate the mobility of Cu ions in Cu-exchanged zeolites, revealing that aluminum pairing accelerates local hopping dynamics and increased NH3 concentration enhances long-range diffusion of Cu ions. Furthermore, the probability of finding metal complexes in the same cage increases with higher Cu and Al content.
ACS CENTRAL SCIENCE
(2023)
Editorial Material
Chemistry, Physical
Mercedes Boronat
Summary: This article investigates the impact of zeolite framework topology on catalyst performance and proposes new strategies for improved material design.
Review
Chemistry, Multidisciplinary
Lichen Liu, Avelino Corma
Summary: Heterogeneous bimetallic catalysts are widely used in industrial processes, but understanding the active sites in these catalysts at the atomic and molecular level is challenging due to their structural complexity. Comparing the structural features and catalytic performances of different bimetallic entities can aid in developing a unified understanding of the structure-reactivity relationships and improving current bimetallic catalysts. This review discusses the geometric and electronic structures of three representative types of bimetallic catalysts, as well as the synthesis methods, characterization techniques, and catalytic applications of these catalysts.
Article
Chemistry, Physical
Risheng Bai, Yue Song, Ge Tian, Fei Wang, Avelino Corma, Jihong Yu
Summary: The synthesis of highly efficient nano-sized Ti-rich TS-1 zeolites with controllable titanium species is crucial in zeolite catalytic reactions. A new method was developed using tetrabutyl orthotitanate tetramer as the titanium source, which slowed down the zeolite crystallization process and prevented the formation of anatase species. The Ti-rich TS-1 zeolite prepared with this method exhibited enriched active titanium species, enlarged external surface area, and superior catalytic performance in oxidative desulfurization reactions.
GREEN ENERGY & ENVIRONMENT
(2023)
Review
Chemistry, Multidisciplinary
Alexandra Velty, Avelino Corma
Summary: For many years, capturing, storing or sequestering CO2 from emission sources has been an effective method for reducing atmospheric CO2. The chemical conversion of CO2 into valuable chemicals has gained much attention due to CO2's abundance and renewable nature. Catalysts, particularly zeolite and ordered mesoporous materials, play a critical role in the conversion of CO2. By studying the reactions involving these catalysts, this review aims to explore the potential opportunities for using them to convert CO2 into essential chemicals and fuels.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Physical
Joaquin Martinez-Ortigosa, Reisel Millan, Jorge Simancas, Manuel Hernandez-Rodriguez, J. Alejandro Vidal-Moya, Jose L. Jorda, Charlotte Martineau-Corcos, Vincent Sarou-Kanian, Mercedes Boronat, Teresa Blasco, Fernando Rey
Summary: This study investigates the synthesis of all-silica RTH zeolites using triisopropyl(methyl)phosphonium as the organic SDA. The results show the formation of two distinct crystalline phases under different synthesis conditions, with fluoride bonding to different silicon sites. It demonstrates the possibility of controlling the placement of fluoride in RTH zeolites through synthesis conditions.
JOURNAL OF MATERIALS CHEMISTRY A
(2024)
