Article
Chemistry, Multidisciplinary
Mengyuan Chen, Yuchen Liang, Taotao Dong, Weijian Liang, Yanping Liu, Yage Zhang, Xin Huang, Lichun Kong, Zhi-Xiang Wang, Bo Peng
Summary: The study merged the Morita-Baylis-Hillman (MBH) reaction and the [3,3]-sigmatropic rearrangement to achieve the [3,3]-rearrangement of aryl sulfoxides with alpha,beta-unsaturated nitriles, offering a new approach to prepare alpha-aryl alpha,beta-unsaturated nitriles with Z-selectivity. Control experiments and DFT calculations support a four-stage reaction sequence, including assembly, Lewis base addition, rearrangement, and E1cB-elimination, explaining the remarkable Z-selectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shuai Zhang, Nan Jiang, Jun-Zhao Xiao, Guo-Qiang Lin, Liang Yin
Summary: A copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported, providing a range of highly selective phosphine derivatives. The method shows broad substrate scope and the high stereoselectivity is attributed to the stability of the Cu(I)-(R,R)-QUINOXP* complex and its asymmetric induction. Finally, the method is used for the synthesis of new chiral phosphine-olefin compounds, one of which serves as a wonderful ligand in Rh-catalyzed asymmetric conjugate addition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shuai Zhang, Nan Jiang, Jun-Zhao Xiao, Guo-Qiang Lin, Liang Yin
Summary: Herein, a copper(I)-catalyzed asymmetric hydrophosphination method for 3,3-disubstituted cyclopropenes is reported. The method provides phosphine derivatives with high diastereo- and enantioselectivities. It has a broad substrate scope and the high stereoselectivity is attributed to the stability and asymmetric induction of the Cu(I)-(R,R)-QUINOXP* complex. The method is also used for the synthesis of new chiral phosphine-olefin compounds, which serve as ligands in Rh-catalyzed asymmetric conjugate addition reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zixuan Tong, Olivia L. Garry, Philip J. Smith, Yubo Jiang, Steven J. Mansfield, Edward A. Anderson
Summary: This study reports a gold-catalyzed oxidative functionalization reaction to access unnatural amino acid derivatives using a wide range of nucleophiles. The reaction proceeds under mild conditions with high functional group tolerance, and displays excellent regioselectivity through subtle steric differentiation of the yndiamide nitrogen atom substituents.
Article
Chemistry, Organic
Weiping Zhou, Arnaud Voituriez
Summary: The asymmetric total synthesis of two sesquiterpenoids, (-)-HM-3 and (-)-HM-4, isolated from a phytopathogenic fungus, has been achieved using a gold-catalyzed [3,3]-sigmatropic rearrangement of sulfonium as a key step. A high enantiomeric excess of 96% was observed in the chirality transfer from the chiral sulfoxide substrate to the newly formed quaternary stereogenic center. The implementation of this efficient methodology enabled the isolation of the two natural products in just 7-8 chemical steps with overall yields of 12-16%.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Zheyuan Liu, Xiaojiao Jin, Yanfeng Dang
Summary: Density functional theory calculations have revealed the mechanism and origin of regio- and stereoselectivity in [2,3]-sigmatropic rearrangements of diazoesters with allylic iodides/sulfides via chiral bisoxazoline-Cu(I) catalysts. Different reaction pathways were observed for iodonium and sulfonium ylides due to substrate-ligand steric repulsions. The regioselectivity is derived from the electronic effect of phenyl on the charge distribution over the allyl moiety, while the stereoselectivity is mainly controlled by substrate-ligand steric interactions.
Article
Chemistry, Multidisciplinary
Chao Ning, Kang-Hua Rui, Yin Wei, Min Shi
Summary: In this study, the mechanism of Rh(i) complex catalyzed dimerization of ene-vinylidenecyclopropanes was elucidated through experimental and computational studies, and a key intermediate was identified.
Article
Chemistry, Multidisciplinary
Hye Won Moon, Feng Wang, Kalishankar Bhattacharyya, Oriol Planas, Markus Leutzsch, Nils Noethling, Alexander A. Auer, Josep Cornella
Summary: This research investigates the transfer hydrogenation of azoarenes catalyzed by bismuth through experimental and computational studies. The role of protic and hydridic hydrogens in the reaction is identified through kinetic analysis and reactivity studies using p-trifluoromethylphenol and pinacolborane. The possibility of bismuth-ligand cooperativity is also assessed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Croix J. Laconsay, Dean J. Tantillo
Summary: Density functional theory calculations were employed to study metal-catalyzed [2,3]-rearrangements, revealing that the dissociation of metal catalyst is primarily influenced by the steric bulkiness of adjacent functional groups.
Article
Chemistry, Multidisciplinary
Ebbin Joseph, Rafael D. Hernandez, Jon A. Tunge
Summary: Sustainable catalysis: The development of a cobalt-catalyzed decarboxylative allylation of nitrophenyl alkanes, nitroalkanes, and ketones is accomplished. The protocol offers the regioselective synthesis of various allylated products with broad functional group tolerance. Mechanistic studies revealed an unusual activation of Co(II)-salts using new organoreductants.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ya-Qian Zhang, Xue-Yu Han, Yue Wu, Peng-Jia Qi, Qing Zhang, Qing-Wei Zhang
Summary: In this study, a highly regio- and enantioselective hydrophosphinylation reaction of secondary phosphine oxides and enynes was achieved through Ni catalysis. A new mechanism was discovered through kinetic studies and DFT calculations. The alkene moiety played a vital role in the reactivity, regio-, and enantioselectivity.
Review
Chemistry, Multidisciplinary
Anna Roglans, Anna Pla-Quintana, Miquel Sola
Summary: The review in this article covers the mechanistic aspects of the transition-metal-catalyzed [2 + 2 + 2] cycloaddition reaction involving various unsaturated substrates with metals such as Co, Ni, Ru, Rh, Ir, Pd, etc. It provides an overview from the early studies to the present day, focusing on the key mechanistic aspects that influence reactivity and selectivity, comparing different unsaturated substrates and transition metals used.
Article
Chemistry, Organic
Jiang Zhu, Jiaji Li, Lianjie Zhang, Shitao Sun, Lu Yang, Jiayue Fu, Hanyang Sun, Maosheng Cheng, Bin Lin, Yongxiang Liu
Summary: Spiro[indoline-3,3′-pyrrolidine] and spiro[indoline-3,3′-piperidine] derivatives were synthesized in a substitution-controlled manner using cationic gold(I) catalyst and Hantzsch ester (HEH). The optimal reaction conditions were determined by screening, and the functional group tolerances of these pathways were examined using synthetic substrates. Density functional theory calculations elucidated the endo and exo selectivities of these cyclizations, and a plausible mechanism for these transformations was proposed.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Abing Duan, Fengjiao Xiao, Yu Lan, Linbin Niu
Summary: This review summarizes the representative advancements in theoretical studies on transition-metal-catalyzed reductive coupling reactions, focusing on the mechanisms of key steps and the activation modes of electrophiles, as well as the generation of selectivity. The mechanism of the reduction of high-oxidation-state catalysts and the construction of new chemical bonds are also discussed.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Jiang Zhu, Jiaji Li, Lianjie Zhang, Shitao Sun, Zhaobo Wang, Xiang Li, Lu Yang, Maosheng Cheng, Bin Lin, Yongxiang Liu
Summary: Density functional theory calculations were used to predict the pathways of gold(I)-catalyzed cycloisomerization of indole substrates with 1,6-enynes, which were consistent with experimental results. The substitution-controlled synthesis allowed for tunable formation of 1H-pyrido[4,3-b]indole and spiro[indoline-3,3'-pyridine] derivatives. The reactions exhibited good functional group tolerances, and a possible mechanism was proposed based on computational and experimental results.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel C. Elliott, Alex Marti, Pablo Mauleon, Andreas Pfaltz
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Multidisciplinary
Suhong Kim, F. Dean Toste
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Trandon A. Bender, Mariko Morimoto, Robert G. Bergman, Kenneth N. Raymond, F. Dean Toste
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Yongseok Kwon, Junqi Li, Jolene P. Reid, Jennifer M. Crawford, Roxane Jacob, Matthew S. Sigman, F. Dean Toste, Scott J. Miller
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
Javier Corpas, M. Teresa Quiros, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Article
Chemistry, Organic
Javier Corpas, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Review
Chemistry, Physical
Javier Corpas, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: This paper discusses the importance of the catalytic functionalization of alkynes with organoboron reagents in synthesis and the latest research progress, including innovations in asymmetric internal alkynes, stereochemistry, and metal migration. It focuses on the practicality, limitations, and challenges for future research of the mechanisms and synthetic methods.
Article
Chemistry, Multidisciplinary
Shin-Ho Kim-Lee, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: A novel dual Cu catalysis strategy based on a dynamic multiligand coordination pool is described, triggering cooperative polar/radical pathways in a single catalytic cycle. This strategy overcomes the reactivity issue in Cu-catalyzed carboboration, expanding the scope of the reaction and opening avenues to access stereodefined tetrasubstituted vinylboronates.
Article
Engineering, Chemical
I Salmeron-Sanchez, J. Asenjo-Pascual, J. R. Aviles-Moreno, J. C. Perez-Flores, P. Mauleon, P. Ocon
Summary: This study modified four commercially available ion exchange membranes to reduce the crossover phenomena of redox active species in AORFB systems. The modified membranes showed optimal properties with minimal impact on ion conductivity, making them appealing for AORFB applications. Additionally, the modified anionic exchange membranes demonstrated increased ion exchange capacity and greater double layer stability compared to cationic exchange membranes.
JOURNAL OF MEMBRANE SCIENCE
(2022)
Article
Chemistry, Physical
Javier Corpas, Enrique M. Arpa, Romain Lapierre, Ines Corral, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: The cooperative action of the acetate ligand, the 2-pyridyl sulfonyl directing group, and the palladium catalyst is crucial for controlling reactivity, regioselectivity, and stereoselectivity in the acetoxylation of unsymmetrical internal alkynes. Insight into the roles of the acetate ligand in the reaction mechanism is provided by experimental and computational analyses, contributing to a better understanding of the observed regiocontrol.
Article
Chemistry, Multidisciplinary
Javier Corpas, Miguel Gomez-Mendoza, Jonathan Ramirez-Cardenas, Victor A. . de la Pena O'Shea, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: A dual catalyst system based on the ligand exchange of two diphosphine ligands in a copper complex has been developed for the merging of metal- and photocatalytic activation modes. This system has been successfully applied to the formal antihydroboration of activated internal alkynes. Photochemical studies have characterized the photoactive species and investigated the interaction between the catalysts, shedding light on the mechanism of the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Juan Asenjo-Pascual, Ivan Salmeron-Sanchez, Pablo Mauleon, Maddalen Agirre, Ana Catarina Lopes, Oihane Zugazua, Eduardo Sanchez-Diez, Juan Ramon Aviles-Moreno, Pilar Ocon
Summary: In this study, a computational predictive tool for redox flow batteries is presented and supported by experimental evidence. A DFT protocol is successfully used to predict the stability and potential application of non-planar bipyridinium salts as active materials in Aqueous Organic Redox Flow Batteries (AORFB). The NBO and ADCH charge analyses help understand the stability of the reduced species and the importance of molecular design for AORFB electrolyte stability.
JOURNAL OF POWER SOURCES
(2023)
Article
Nanoscience & Nanotechnology
Juan Asenjo-Pascual, Cedrik Wiberg, Mahsa Shahsavan, Ivan Salmeron-Sanchez, Pablo Mauleon, Juan Ramon Aviles Moreno, Pilar Ocon, Pekka Peljo
Summary: A highly soluble triazine derivative (SPr)(3)4TpyTz with three reversible redox processes and fast kinetics has been synthesized using a cost-effective and straightforward method. Concentrated single cell tests and DFT studies revealed a tendency of the reduced triazine species to form aggregates, which can be avoided by adjusting the electrolyte concentration. Under optimal conditions, (SPr)(3)4TpyTz exhibited no capacity decay, good Coulombic efficiency, voltage efficiency, and energy efficiency for the storage of two electrons. However, the storage of additional electrons led to capacity decay and an increase in electrolyte pH, indicating irreversible protonation of the generated species. A possible mechanism has been proposed. Higher concentrations of (SPr)(3)4TpyTz showed slightly higher capacity decay and lower efficiencies due to aggregate formation.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Review
Chemistry, Multidisciplinary
Javier Corpas, Shin-Ho Kim-Lee, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: The exceptional versatility of sulfones has been extensively utilized in organic synthesis, particularly in catalytic desulfitative functionalizations. This review discusses new facets of sulfone reactivity, emphasizing key mechanistic features, and explores the potential application of this technology in the synthesis of natural products.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Angela C. Stelson, Cynthia M. Hong, Mitchell C. Groenenboom, Charles A. E. Little, James C. Booth, Nathan D. Orloff, Robert G. Bergman, Kenneth N. Raymond, Kathleen A. Schwarz, F. Dean Toste, Christian J. Long
COMMUNICATIONS CHEMISTRY
(2019)
