Article
Chemistry, Inorganic & Nuclear
Illia Ruzhylo, Alix Sournia-Saquet, Alain Moreau, Tom Delord, Eric Manoury, Rinaldo Poli, Agnes Labande
Summary: A series of heteroleptic dirhodium(II) complexes with a redox-active ferrocenecarboxylate ligand were synthesized and characterized. It was found that the oxidation of the ferrocenecarboxylate ligand has an effect on the chemoselectivity of the dirhodium-catalyzed diazo decomposition. This study provides a new strategy for tuning the electronic properties of complexes without ligand exchange.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Min Liu, Kelu Yan, Jiangwei Wen, Xue Li, Xiaoyu Wang, Fengjie Lu, Xiu Wang, Hua Wang
Summary: The rhodium(III)-catalyzed C-H/diazo coupling and tandem annulation of 3-oxopent-4-enenitriles have been proposed for the synthesis of polysubstituted phenols, yielding most products in good yields. Preliminary mechanistic studies and derivatization reactions of phenol products were also conducted, offering an alternative approach for synthesizing a variety of useful phenols.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Jianwei Xie, Li Wu, Ping Lu, Yanguang Wang
Summary: In this study, stereoselective synthesis of (E)-3-arylideneindolin-2-imines was achieved using copper bromide as the catalyst. The olefination reaction proceeded through copper-catalyzed aerobic oxidation of hydrazones to diazo compounds and copper-catalyzed cross coupling of two different diazo components in a tandem manner.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Pooja Soam, Priya Kamboj, Vikas Tyagi
Summary: This review discusses the use of diazo compounds as carbene precursors in synthetic chemistry, particularly focusing on the generation of metal bound carbenes with the help of metal catalysts, with rhodium being a widely used catalyst for cascade reactions involving carbene transfer. The efforts made in the past five years towards the synthesis of important heterocyclic compounds through rhodium-catalyzed cascade reactions are also covered in this review.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Anae I. Bain, Kiran Chinthapally, Arianne C. Hunter, Indrajeet Sharma
Summary: Dual catalysis is a more efficient method in carbene chemistry that improves the efficiency of existing reactions and enables new chemical transformations. Reactions involving dual synergistic catalysis offer convenient strategies for synthesizing challenging quaternary carbon centers and bioactive core structures.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Cai Zhang, Jie-Ping Wan
Summary: Diazomethyl-substituted iodine(III) compounds with electron-withdrawing groups have potential reaction abilities and can be used as key intermediates in organic synthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Inorganic & Nuclear
Feifei Li, Longqiang Xiao, Bang Li, Xingyi Hu, Lijian Liu
Summary: Carbene polymerization is a unique nonpetroleum-based polymerization pathway with broad applications. Over the past 20 years, significant progress has been made in the study of carbene polymerization, including efficient initiating systems, high molecular weight and stereoregular polycarbene, and controlled polymerization methods.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Nicholas J. Porter, Emma Danelius, Tamir Gonen, Frances H. Arnold
Summary: This study developed a catalyst that uses diazirines as carbene precursors, providing a new strategy for selective carbene transfer. By engineering variants of ApePgb protoglobin, selective carbene transfer from diazirines can be achieved at room temperature. The structure of an ApePgb variant, determined by microcrystal electron diffraction, revealed how evolution has enhanced access to the heme active site for this new-to-nature catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Julia O. Strelnikova, Nikolai Rostovskii, Olesya Khoroshilova, Alexander F. Khlebnikov, Mikhail S. Novikov
Summary: A high-yielding method for synthesizing 2H-1,3,5-oxadiazines by the rhodium(II)- or copper(II)-catalyzed reaction of 1,2,4-oxadiazoles with alpha-diazo esters has been developed, where the N2-attack and N4-attack of the carbenoid cause different oxadiazole ring openings controlled by the substitution at C5.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Junrong Chen, Muhammad Suleman, Ping Lu, Yanguang Wang
Summary: A Rh(III)-catalyzed [4+1] annulation of aromatic carboxylic acids with 4-diazoisoquinolin-3-ones was reported. A library of highly substituted spiro [isobenzofuran-1,4'-isoquinoline]-3,3'-diones were synthesized in moderate to good yields by this protocol (30 examples, up to 84% yield). The merits of this protocol are broad substrate scope, readily available starting materials, mild reaction conditions, and scalability.
Article
Chemistry, Applied
Taylor A. Hatridge, Bo Wei, Huw M. L. Davies, Christopher W. Jones
Summary: This study demonstrates the efficient synthesis of diazo compounds through copper-catalyzed hydrazone oxidation in a continuous flow reactor, showcasing its utility in various reactions such as alkene cycloaddition. The process exhibits robustness, high selectivity, and improvement over previous non-catalytic methods, aiming to reduce waste and enhance practicality.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Physical
Wenbin Liu, Jack Twilton, Bo Wei, Maizie Lee, Melissa N. Hopkins, John Bacsa, Shannon S. Stahl, Huw M. L. Davies
Summary: A mild method for accessing diazo compounds via aerobic oxidation of hydrazones was described, using a Cu(OAc)(2)/pyridine catalyst and molecular oxygen. Insight gained from mechanistic studies led to the expansion of this method to include diaryl hydrazones, delivering diaryl diazomethane derivatives. The products can be used in rhodium carbene catalysis without isolation of the diazo intermediate to afford cyclopropane products in good yield with high enantioselectivity.
Article
Chemistry, Physical
Aoife M. Buckley, Daniel C. Crowley, Thomas A. Brouder, Alan Ford, U. B. Rao Khandavilli, Simon E. Lawrence, Anita R. Maguire
Summary: A new class of dirhodium carboxylate catalysts, derived from specific 2-fenchyloxy or 2-menthyloxy arylacetic acids, have shown excellent enantioselectivity and trans diastereoselectivity across a range of transformations. These catalysts are highly efficient in various reactions, such as C-H insertion, intramolecular aromatic addition, and oxonium ylide formation and rearrangement, displaying up to 93% ee in product yield.
Article
Chemistry, Organic
Matthew L. Martin, Alistair Boyer
Summary: N-2-Sulfonyl-alpha-diazo amidines can be synthesized through the 1,3-dipolar cycloaddition reaction with excellent regioselectivity. The use of electron poor nitrobenzenesulfonyl group and large carboxylate rhodium ligands allows for controlling the outcome and selecting for 1,2-H shift, resulting in high yielding and excellent Z-selectivity of alpha,beta-unsaturated amidines.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Joshua K. Sailer, Jack C. Sharland, John Bacsa, Caleb F. Harris, John F. Berry, Djamaladdin G. Musaev, Huw M. L. Davies
Summary: A series of chiral bowl-shaped diruthenium(II,III) tetracarboxylate catalysts were prepared for asymmetric cyclopropanation reactions. These diruthenium catalysts self-assembled to form C(4)-symmetric bowl-shaped structures, similar to their dirhodium counterparts. The best catalyst, Ru-2(S-TPPTTL)(4)& BULL;BArF, achieved up to 94% ee in the cyclopropanation of various substrates. In contrast, the copper and cobalt congeners produced catalysts with little to no asymmetric induction. Computational studies revealed that the carbene complexes of the dicopper and dicobalt systems were prone to losing carboxylate ligands, which are essential for the bowl-shaped structure critical for asymmetric induction.
Article
Chemistry, Multidisciplinary
Giulia Giubertoni, Gijs Rombouts, Federico Caporaletti, Antoine Deblais, Rianne van Diest, Joost N. H. Reek, Daniel Bonn, Sander Woutersen
Summary: Inspired by NMR, IR-DOSY is a technique that characterizes both molecular structure and size using infrared spectroscopy. It achieves sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration. Molecules with different sizes are separated into distinct sets of IR peaks in the IR-DOSY spectrum. The 3D-IR-DOSY combines conformation sensitivity with size sensitivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
T. Bouwens, T. M. A. Bakker, K. Zhu, J. Hasenack, M. Dieperink, A. M. Brouwer, A. Huijser, S. Mathew, J. N. H. Reek
Summary: Inspired by natural photosynthesis, we use supramolecular machinery to inhibit electron-hole recombination in molecular photoelectrochemical devices, resulting in an increase in power conversion efficiency.
Article
Chemistry, Organic
Flip Holtrop, Christoph Helling, Martin Lutz, Nicolaas P. van Leest, Bas de Bruin, J. Chris Slootweg
Summary: We present a combined theoretical and experimental investigation on the potential isolation of an encounter complex enabled by enhancement of London dispersion forces between a sterically encumbered Lewis acid and base pair. The study involved the bulky triarylamine N(3,5-tBu(2)C(6)H(3))(3) and the novel triarylborane B(3,5-tBu(2)C(6)H(3))(3), leading to the isolation of a 1:1 co-crystal of both FLP components.
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Katharina Konieczny, Felix J. de Zwart, Eduard. O. Bobylev, Eszter Barath, Sergey Tin, Bernd H. Mueller, Joost N. H. Reek, Bas de Bruin, Johannes G. de Vries
Summary: Researchers achieved enantioselective hydrogenation of cyclic enamides using an earth-abundant cobalt-bisphosphine catalyst. The catalytic system, CoCl2/(S,S)-Ph-BPE, reduced trisubstituted carbocyclic enamides to saturated amides with high activity and excellent enantioselectivity (up to 99%). The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations suggested a sigma-bond-metathesis pathway for the hydrogenation of the carbon-carbon double bond, involving a high spin cobalt (II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Catriona C. James, Petrus C. M. Laan, Bas de Bruin, Joost N. H. Reek
Summary: Olefin metathesis catalysts, such as AquaMet, are susceptible to decomposition under biologically relevant conditions. Current stabilizing strategies have limited applicability under these conditions. Encapsulation of AquaMet within a supramolecular metallocage, with nitrate counterions, enhances the catalyst activity. Replacement of AquaMet's chloride ligands with nitrates through simple anion-exchange leads to higher yields of ring-closed product under aqueous and biological conditions. This kinetic protection strategy of transition metal catalysts may find applications in other in vivo catalytic reactions.
Article
Chemistry, Multidisciplinary
Demi D. Snabilie, Eva J. Meeus, Roel F. J. Epping, Zhiyuan He, Minghui Zhou, Bas de Bruin
Summary: Transition metal radical-type carbene transfer catalysis is a sustainable and atom-efficient method for C-C bond formation. Understanding off-cycle and deactivation pathways can lead to solutions for avoiding catalyst deactivation and reveal novel reactivity for new applications, stimulating further development of radical-type carbene transfer reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
David A. Poole III, Eduard O. Bobylev, Bas de Bruin, Simon Mathew, Joost N. H. Reek
Summary: This article investigates the self-assembly of spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands. The self-assembly process is found to be sensitive to the solvents, reagents, and/or reactants used, which hinders the development of desired palladium-based cages. The study reveals that ligand substitution can be facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Roel F. J. Epping, David Vesseur, Minghui Zhou, Bas de Bruin
Summary: Discovered in the 1970s as organometallic curiosities, carbene radicals have become essential in modern homogeneous catalysis. These radicals exhibit nucleophilic reactivity different from electrophilic Fischer carbenes. The successful catalytic application of carbene radicals has led to the synthesis of diverse carbon and heterocyclic compounds. This Perspective provides an overview of the coordination chemistry, reactivity, and catalytic application of carbene radicals using transition metal complexes and catalysts since 2011.
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
Luis Tarifa, M. Pilar del Rio, Laura Asensio, Jose A. Lopez, Miguel A. Ciriano, Ana M. Geer, Cristina Tejel
Summary: A straightforward catalytic method for the synthesis of complex C-substituted piperazines has been developed based on an uncommon head-to-head coupling of easily prepared imines. This efficient process allows the selective formation of a sole diastereoisomer, exhibits a broad substrate scope, and shows good functional group tolerance using a bench-stable iridium catalyst under mild reaction conditions. The addition of N-oxides notably enhances the catalytic activity and selectivity.
Article
Chemistry, Multidisciplinary
M. Pilar del Rio, B. Eva Villarroya, Jose A. Lopez, Ana M. M. Geer, Fernando J. J. Lahoz, Miguel A. A. Ciriano, Cristina Tejel
Summary: This study describes the synthesis of neutral and dicationic tetrametallic iridium chains connected by an iridium-iridium bond. The complexes exhibit fractional averaged oxidation states and electronic delocalization along the metallic chain. The absorption spectra of the complexes show characteristic bands that can be fine-tuned by varying the terminal capping ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Petrus C. M. Laan, Eduard O. Bobylev, Felix J. de Zwart, Joppe A. Vleer, Alessandro Troglia, Roland Bliem, Gadi Rothenberg, Joost N. H. Reek, Ning Yan
Summary: Controlling the coordination sphere of heterogeneous single-metal-site catalysts is a difficult task, but immobilizing supramolecular cages to control the ligand design of the primary- and secondary coordination spheres allows for fine-tuning of catalytic properties. The study of the hydrolysis of ammonia borane revealed that placing a well-defined reaction pocket around the active site can enhance catalytic performance, resulting in diffusion-controlled reaction kinetics.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Subrata Das, Andreas W. Ehlers, Sima Patra, Bas de Bruin, Buddhadeb Chattopadhyay
Summary: A concept for intermolecular C-N cross-coupling amination has been discovered using tetrazoles and aromatic and aliphatic azides with boronic acids under iron-catalyzed conditions. The reaction follows an unprecedented metalloradical activation mechanism, different from traditional metal-catalyzed C-N cross-coupling reactions. The wide scope of this reaction has been demonstrated by employing various tetrazoles, azides, and boronic acids. Moreover, the reaction has shown potential for applications in medicinal chemistry, drug discovery, and pharmaceutical industries, as demonstrated by late-stage aminations and synthesis of a drug candidate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Luis Tarifa, Ana M. Geer, Laura Asensio, Jose A. Lopez, Miguel A. Ciriano, Cristina Tejel
Summary: The ability of a heteroditopic ligand to create separate compartments for metals in different oxidation states has been developed and studied.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Meiling Xu, Bin Sun, David A. Poole III, Eduard O. Bobylev, Xu Jing, Jinguo Wu, Cheng He, Chunying Duan, Joost N. H. Reek
Summary: This study reports an example of supramolecular cages with fixed gold complexes at the windows, showing confinement effects, stability, and enzymatic catalytic characteristics in gold-catalyzed reactions.
