Article
Chemistry, Organic
Bryan C. Figula, D. Lucas Kane, Kaluvu Balaraman, Christian Wolf
Summary: Cross-coupling of alkyl fluorides and organocuprates is achieved via aluminum halide mediated C-F bond activation, leading to the formation of Csp2-Csp3 and Csp3-Csp3 bonds. The reaction exhibits mild conditions and effectively controls competing side reactions, resulting in high yields and good functional group tolerance.
Article
Multidisciplinary Sciences
Wen-Tao Zhao, Jian-Xin Zhang, Bi-Hong Chen, Wei Shu
Summary: This study reports an enantio-selective alkyl-alkyl cross-coupling reaction using a newly-developed chiral tridentate ligand. Two different alkyl halides were successfully cross-coupled to form α-tertiary aliphatic amides. The mechanism investigation revealed that one alkyl halide undergoes oxidative addition with nickel, while the other alkyl halide forms alkyl zinc reagents in situ, enabling reductive alkyl-alkyl cross-coupling without preformation of organometallic reagents.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Ikuya Fujii, Kazuhiko Semba, Yoshiaki Nakao
Summary: Rhodium-aluminum bimetallic complexes catalyze the Kumada-Tamao-Corriu (KTC) cross-coupling reaction using arylmagnesium compounds generated from corresponding aryl fluorides or chlorides. This method allows the challenging KTC coupling reaction to be carried out using aryl fluorides as nucleophiles, resulting in various biaryls.
Article
Chemistry, Organic
Dong-Ping Wu, Wei Ou, Pei-Qiang Huang
Summary: This study describes the catalytic reductive condensation reactions between tertiary amides and active methylene compounds, leading to multifunctionalized non-N-containing products. The reactions proceed through a sequential process involving iridium-catalyzed hydrosilylation of the amides followed by acid-mediated condensation with the active methylene compounds. This scalable method demonstrates a broad scope and remarkable chemoselectivity for the amide group in the presence of various sensitive or even more reactive functionalities such as ester, cyano, nitro, silyl dienol ether, and ketone.
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)
Editorial Material
Chemistry, Organic
Ruben Martin, Gary A. Molander
Summary: Ruben Martin and Gary A. Molander, renowned professors in the field of chemistry from Spain and the United States, respectively, have conducted in-depth research in their respective fields, focusing on developing new synthetic methods and catalytic reactions to provide important technological support for the preparation of high-value compounds.
Article
Chemistry, Multidisciplinary
James L. Douthwaite, Ruheng Zhao, Eunjae Shim, Babak Mahjour, Paul M. Zimmerman, Tim Cernak
Summary: We developed a new reaction method for the cross-coupling of alkyl amines and aryl carboxylic acids, by preactivating the amine-acid building blocks. This reaction forms C-(sp(3))-C-(sp(2)) bonds and shows good yields for various substrates, including pharmaceutical compounds. High-throughput experimentation led to the discovery of performance-enhancing additives such as phthalimide, RuCl3, and GaCl3.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Peter G. N. Neate, Bufan Zhang, Jessica Conforti, William W. Brennessel, Michael L. Neidig
Summary: Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, allowing for diverse coupling reactions without significant modification of the catalytic protocol. This represents a rare example of a single iron-catalyzed system effective across various coupling reactions while remaining operationally simple.
Article
Chemistry, Multidisciplinary
Elwira Bisz, Martina Koston, Michal Szostak
Summary: A new study reported the use of non-toxic and sustainable N-butylpyrrolidone (NBP) as a substitute for reprotoxic N-methylpyrrolidone (NMP) in iron-catalyzed cross-coupling reactions, achieving successful alkylations with high efficiency and broad functional group tolerance. The efficiency of NBP in these reactions surpassed or matched that of NMP, demonstrating potential applications in the synthesis of pharmaceutical intermediates.
Article
Chemistry, Multidisciplinary
Philipp Schueler, Simon Sengupta, Sven Krieck, Matthias Westerhausen
Summary: The alkaline-earth metals Mg and Ca are too inert for the direct metalation of primary and secondary amines. Activation prior to use or the use of Grignard reagents can be alternatives. However, the straightforward synthesis of alkylcalcium reagents has disadvantages due to various side reactions. Reactions of suspensions of magnesium or calcium with amine and ethyl bromide can lead to the formation of RAeX, which can undergo in situ Grignard metalation or addition reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jiahua Chen, Jun Wei Lim, Derek Yiren Ong, Shunsuke Chiba
Summary: The synthesis of alpha-tertiary amines was achieved by iteratively adding carbon nucleophiles to N,N-dialkyl carboxamides, forming anionic tetrahedral carbinolamine intermediates. These intermediates were then treated with bromotrimethylsilane followed by organomagnesium or organolithium reagents to produce alpha-tertiary amines. The use of (trimethylsilyl)methylmagnesium bromide as the second nucleophile allowed for aza-Peterson olefination, resulting in the formation of 1,1-diarylethylenes after acidic work-up.
Article
Chemistry, Multidisciplinary
Daniels Posevins, Aitor Bermejo-Lopez, Jan-E. Backvall
Summary: An iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents was disclosed, allowing for efficient chirality transfer and preparation of various fluoroalkyl allenes. Additionally, an iron-catalyzed cross-coupling of Grignard reagents with alpha-alkynyl oxetanes and tetrahydrofurans was demonstrated as a straightforward approach towards fully substituted beta- or gamma-allenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Marius Deuker, Yang Yang, Richard A. J. O'Hair, Konrad Koszinowski
Summary: The use of silver as a catalyst in cross-coupling reactions has potential, with high-valent species readily undergoing reductive elimination. Experimentally observed trends in reactivity are reproduced by quantum chemical calculations, providing insight into the structures and energetics of the species involved. These findings suggest that silver-mediated cross-coupling reactions can be a viable alternative to established synthetic methods.
Article
Chemistry, Organic
Quentin D. Tercenio, Erik J. Alexanian
Summary: The nickel-catalyzed reductive coupling of allyl alcohols with chiral, nonracemic alkyl tosylates reported in this study delivers valuable allylation products with high levels of stereospecificity across a range of substrates. The catalytic system, consisting of a simple nickel salt and a commercially available reductant, represents a rare example of a cross-coupling involving the C-O bonds of two electrophiles.
Article
Chemistry, Multidisciplinary
Nikki J. Bakas, Pablo Chourreu, Eric Gayon, Guillaume Lefevre, Michael L. Neidig
Summary: The molecular-level role of alkoxide salts as alternative additives in iron-catalyzed cross-coupling reactions is investigated. Spectroscopic studies reveal that alkoxides promote the formation of homoleptic organoferrates, providing a non-toxic alternative to N-methylpyrrolidone for accessing reactive intermediates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Sylvain Sudan, Damien W. Chen, Cesare Berton, Farzaneh Fadaei-Tirani, Kay Severin
Summary: A water-soluble coordination cage with a short PEG chain was synthesized by reacting Pd(NO3)(2) with a 1,3-di(pyridin-3-yl)benzene ligand. The cage exhibited high selectivity for chloride binding and displayed a significantly higher association constant compared to other chloride receptors. The introduction of a fluorinated dipyridyl ligand further enhanced the chloride binding affinity by a factor of 3.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Paul Varava, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Dimitrios A. Pantazis, Gerard P. Van Trieste, David C. Powers, Kay Severin
Summary: In this study, we report the structural characterization of copper complexes with both bridging and terminal alkenylidene ligands. The complexes were obtained by irradiation of Cu-I complexes with N-heterocyclic diazoolefin ligands. The isolation and structural characterization of the complex with a terminal alkenylidene ligand were achieved through crystalline matrix isolation and in crystallo photolysis at low temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Fang-Che Hsueh, Thayalan Rajeshkumar, Bastiaan Kooij, Rosario Scopelliti, Kay Severin, Laurent Maron, Ivica Zivkovic, Marinella Mazzanti
Summary: We report two unique thorium arenide complexes prepared by reduction of a Th-IV-siloxide complex in presence of naphthalene. The stored electrons in these complexes enable the reduction of a broad range of substrates. The reactivity can be tuned by the arenide binding mode, as shown in the reaction of complex 1 with diazoolefin IDipp=CN2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Paul Varava, Tak Hin Wong, Zhaowen Dong, Anastasia Yu. Gitlina, Andrzej Sienkiewicz, Wolfram Feuerstein, Rosario Scopelliti, Farzaneh Fadaei-Tirani, Kay Severin
Summary: The head-to-tail dimerization of N-heterocyclic diazoolefins is discussed, leading to the formation of strongly reducing quinoidal tetrazines. The oxidation of these tetrazines occurs stepwise, resulting in the isolation of a stable radical cation and diamagnetic dications. The latter can also be obtained by oxidative dimerization of diazoolefins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Organic
Xiao-Feng Wu, Paul J. Dyson, Bruce A. Arndtsen
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Lorenzo Pietracci, Riccardo Pettinari, Alessia Tombesi, Fabio Marchetti, Claudio Pettinari, Agustiïn Galindo, Farzaneh Fadaei-Tirani, Mouna Hadiji, Paul J. Dyson
Summary: This study investigates the coordination mechanisms of pyrazolone ligands containing a pyridine ring with the (Ru(II)) fragment through experimental and theoretical calculations. The ligands were found to coordinate in an unusual N,O-chelating fashion with Ru(II), and various complexes were synthesized. The study provides important insights into the properties of the ligands and complexes.
Article
Chemistry, Inorganic & Nuclear
Alfonso Annunziata, Maria Elena Cucciolito, Maddalena Di Ronza, Giarita Ferraro, Mouna Hadiji, Antonello Merlino, Daniel Ortiz, Rosario Scopelliti, Farzaneh Fadaei Tirani, Paul J. Dyson, Francesco Ruffo
Summary: This article reports a series of Ruthenium(II) complexes with a three-legged piano-stool structure based on an arene ring and an N-heterocyclic carbene(NHC)-carbene ligand with a peracetylated glucose moiety. The complexes undergo hydrolysis in water and show reactivity towards model nucleophiles and biological macromolecules. However, they exhibit low anti-tumor activity against human ovarian carcinoma cells and cisplatin-resistant cells.
Article
Chemistry, Multidisciplinary
Shunlin Zhang, Yuxin Xie, Rosie J. J. Somerville, Farzaneh Fadaei Tirani, Rosario Scopelliti, Zhaofu Fei, Dunru Zhu, Paul J. J. Dyson
Summary: This study reports a new family of proton conductors based on MIL-101 and protic ionic liquid polymers (PILPs) containing different anions. The PILP@MIL-101 composites maintain the nanoporous cavities and water stability of MIL-101, while providing much-improved proton transport. The PILP@MIL-101 composite with HSO4- anions shows superprotonic conductivity (6.3 x 10(-2) S cm(-1)) at 85 degrees C and 98% relative humidity.
Article
Chemistry, Multidisciplinary
Haodan Guo, Yanyan Fang, Yan Lei, Jinpeng Wu, Minghua Li, Xiangrong Li, Hong Bo Cheng, Yuan Lin, Paul J. Dyson
Summary: This study demonstrates the use of a self-assembled ionic insulating layer to improve the performance of wide-bandgap perovskite solar cells. The layer effectively suppresses halide phase separation, reducing open-circuit voltage loss and improving device stability.
Article
Multidisciplinary Sciences
Mingyang Liu, Paul J. Dyson
Summary: Efficient valorization of lignin, a sustainable and renewable source, is essential for reducing dependence on fossil-derived feedstocks. This study presents a highly efficient strategy for extracting aromatic monomers and generating functionalized diaryl ethers from lignin using oxidative cross-coupling reactions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Zhaowen Dong, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Kay Severin
Summary: Bent (hetero)allenes, such as carbodicarbenes and carbodiphosphoranes, have diverse applications in coordination chemistry as neutral C-donor ligands. N-Heterocyclic diazoolefins function similarly to L-type ligands, and in this study, the synthesis and reactivity of anionic diazoolefin are described. The anionic diazoolefin displays distinct reactivity, allowing for the preparation of diazo compounds via protonation, alkylation, or silylation. It can also be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes, resulting in the formation of a stable phosphinocarbene through the extrusion of dinitrogen.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Gabriela Gastelu, Pritha Saha, Paul J. Dyson, Martin Hulla, Jorge G. Uranga
Summary: Autocatalytic reactions play a key role in the beginning of life and carbon capture and utilization, providing inspiration for the development of advanced systems for the synthesis of value-added chemicals.
Article
Chemistry, Inorganic & Nuclear
Sarah A. P. Pereira, Jan Romano-deGea, Ana Isabel Barbosa, Sofia A. Costa A. Lima, Paul J. J. Dyson, M. Lucia M. F. S. Saraiva
Summary: The study demonstrates that ruthenium-based compounds, especially [Ru(& eta;(6)-toluene)(PPh3)(2)Cl]Cl, show high selectivity and cytotoxicity against breast cancer cells. This compound has potential as a promising candidate for breast cancer treatment.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Sylvain Sudan, Farzaneh Fadaei-Tirani, Kay Severin
Summary: A penta-stranded helicate was synthesized by combining [Pd(CH3CN)(4)](BF4)(2) with La(NO3)(3) and a polydentate ligand. The helicate exhibited low symmetry in both solution and solid state. By adjusting the metal-to-ligand ratio, a dynamic interconversion between the penta-stranded helicate and a symmetrical, four-stranded helicate was achieved.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Anastasia Yu. Gitlina, Farzaneh Fadaei-Tirani, Kay Severin
Summary: The isomerization of iridium(iii) complexes with metalated N-heterocyclic carbene (NHC) ligands was investigated. The fac isomers of complexes with 1-phenyl-3-methylbenzimidazolin-2-ylidene or 1-phenyl-3-benzylbenzimidazolin-2-ylidene ligands can be cleanly transformed into the mer isomers using HNTf2 and then NEt3. However, an iridium complex with a 1-phenyl-1,2,4-triazolo[4,3-f]phenanthridine-based carbene ligand could not undergo isomerization under similar conditions.
DALTON TRANSACTIONS
(2023)