Article
Chemistry, Multidisciplinary
Ken-Loon Choo, Bijan Mirabi, Karl Z. Demmans, Mark Lautens
Summary: Enantioenriched spiro-oxiranes with three contiguous stereocenters were synthesized using a rhodium-catalyzed cascade reaction, enabling the formation of a spirocyclic framework in a single step. Both sp(2)- and sp-hybridized carbon nucleophiles were found to be efficient initiators, yielding products with different functional groups. Derivatization studies demonstrated the synthetic versatility of the products' epoxide and alkyne moieties. DFT calculations were employed to explain spectroscopic discrepancies between solution- and solid-state structures of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Peng Lu, Hongliang Wang, Yihui Mao, Xin Hong, Zhan Lu
Summary: Investigation on asymmetric hydrogenation of olefins is vital for the synthesis of pharmaceutical molecules and chemical industry. A cobalt-catalyzed enantioconvergent hydrogenation method has been developed for common minimally functionalized E/Z-olefin mixtures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Raja K. K. Rit, Hongyi Li, Stephen P. P. Argent, Katherine M. M. Wheelhouse, Simon Woodward, Hon Wai Lam
Summary: Chiral dienes are important ligands in asymmetric catalysis but they are difficult to obtain. In this study, a simple chiral allenecarboxanilide was used to produce pseudoenantiomeric bicyclo[2.2.2]octa-2,5-dienes containing an alkenyl bromide via intramolecular [4+2] cycloaddition. These compounds can be easily functionalized to provide diverse chiral diene ligands. The synthesis is straightforward and can be conducted on a large scale. The resulting ligands exhibit high performance in nine types of enantioselective Rh(I)-catalyzed addition reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Zhengyu Han, Gang Liu, Xuanliang Yang, Xiu-Qin Dong, Xumu Zhang
Summary: The study developed an efficient and simple synthetic strategy for obtaining both enantiomers of chiral tetrahydroquinoline derivatives through the adjustment of reaction solvents. Gram-scale asymmetric hydrogenation proceeded well with low-catalyst loading, and a possible reaction process was revealed based on various experiments conducted.
Article
Chemistry, Inorganic & Nuclear
Kristina Zivkovic, Lilia M. Baldauf, Jessica L. Cryder, Alexa Villasenor, Valeria Reyes, Lauren E. Bernier, Theresa J. Thomas, Maxwell O'Toole, Kayleen Fulton, Curtis E. Moore, Arnold L. Rheingold, Christopher J. A. Daley
Summary: The study reports the first isolation and structural characterization of a series of chiral trinitrogen pincer ligands, as well as the methods for their preparation. Experimental results show that a novel microwave-based technique is more efficient, although currently not scalable.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Yun-Xuan Tan, Xing-Yu Liu, Cheng-Yu He, Ping Tian
Summary: This study presents a Rh(III)-catalyzed asymmetric carboboration of heterobicyclic alkenes, including 7-oxa- and 7-azabenzonorbornadienes, achieving the transformation with high yields and excellent enantioselectivities. The product bearing seven chiral centers was efficiently obtained, and several transformations of the carboboration product were also demonstrated.
Article
Chemistry, Multidisciplinary
Ryota Shimotsukue, Kohei Fujii, Yu Sato, Yuki Nagashima, Ken Tanaka
Summary: We have developed a rhodium-catalyzed intermolecular [2+2+2] cycloaddition reaction with excellent selectivity, producing chiral cyclohexadienylamines. The reaction involves the reaction of two arylacetylenes with a cis-enamide or a silylacetylene to yield the desired products with complete regio- and diastereoselectivity and high yields and enantioselectivity. Mechanistic studies suggest the formation of a rhodacyclopentadiene intermediate from the terminal alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Dezheng Xie, Ziyi Chen, Chun-Jiang Wang, Xiu-Qin Dong
Summary: Phosphonates and derivatives with an α-chiral center are important compounds found in natural products, pharmaceuticals, and agrochemicals. The synthesis of these compounds has been the focus of recent research, with advancements in asymmetric catalysis such as hydrogenation, addition reactions, and nucleophilic additions to α,β-unsaturated phosphonates. The continuous development of enantioselective catalytic methods and the future applications of these compounds are also discussed.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Applied
Nora Jannsen, Cornelia Pribbenow, Carmen Selle, Hans-Joachim Drexler, Marc-Andre Mueller, Jonathan A. Medlock, Werner Bonrath, Detlef Heller
Summary: An efficient and highly selective semi-hydrogenation of terminal alkynes to alkenes has been achieved using neutral dimeric rhodium(I) complexes. The results show excellent selectivity and no deactivation or reduction in selectivity, indicating the potential industrial application of homogeneous rhodium complexes in the semi-hydrogenation of terminal alkynes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Chantal J. Abou-Fayssal, Christophe Fliedel, Rinaldo Poli, Anders Riisager, Karine Philippot, Eric Manoury
Summary: This study introduces a method to improve the confinement of rhodium nanoparticles (RhNPs) in nanoreactors by introducing phosphine oxide as anchoring groups in the hydrophobic core of amphiphilic star-block copolymers. The RhNP-loaded latex exhibits excellent catalytic activity and recyclability, making it a promising candidate for aqueous biphasic catalysis.
MATERIALS TODAY CHEMISTRY
(2023)
Article
Chemistry, Organic
Bram B. C. Peters, Norman Birke, Luca Massaro, Pher G. Andersson
Summary: The catalytic asymmetric hydrogenation of olefins is a powerful method for synthesizing chiral compounds. By using an iridium N,P-complex catalyst, various prochiral unsaturated amides can be efficiently reduced with high enantioselectivities. The attractive features of this method include its application in the synthesis of fenpropidin and the potential use of isomeric mixtures as starting materials.
Review
Chemistry, Organic
Peng Lu, Zhan Lu
Summary: Transition-metal-catalyzed asymmetric hydrogenation is an important tool for the synthesis of chiral compounds. However, the use of earth-abundant transition metals in this reaction is limited but gaining attention due to cost and environmental concerns. This article summarizes the progress, scope, mechanism, and challenges in the catalytic asymmetric hydrogenation of minimally functionalized alkenes using first row transition metals.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Ricardo Molina Betancourt, Lucas Bacheley, Anzhela Karapetyan, Gerard Guillamot, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: The Rh(III)-catalyzed asymmetric reduction of alpha-trifluoromethyl ketones through transfer hydrogenation was developed under mild conditions. It enables a dynamic kinetic resolution process to access a series of enantioenriched cis-trifluoromethyl alcohols. The reaction was performed efficiently in the green solvent 2-MeTHF using HCO2H/Et3N (1 : 1) as the hydrogen source. High yields and excellent diastereo- and enantioselectivities were achieved for the synthesis of CF3-chromanol, CF3-indanol, and CF3-tetralol derivatives.
Article
Chemistry, Physical
Nora Jannsen, Cornelia Pribbenow, Carmen Selle, Ralf Jackstell, Hans-Joachim Drexler, Marc-Andre Muller, Jonathan A. Medlock, Werner Bonrath, Detlef Heller
Summary: The study successfully achieved the selective reduction of terminal alkynes to alkenes using specific rhodium catalysts. Although catalyst deactivation occurs at high concentrations, several strategies were proposed to overcome this deactivation.
Article
Chemistry, Multidisciplinary
Reshma Kokane, Yann Corre, Erhard Kemnitz, Mohan K. Dongare, Francine Agbossou-Niedercorn, Christophe Michon, Shubhangi B. Umbarkar
Summary: The Pd/MgF2-x(OH)(x) palladium catalyst supported on acidic fluorinated magnesium hydroxide exhibited good catalytic activity in hydrogenation reactions, with the support's acid sites playing a key role in pre-activating N-heterocycle substrates. Additionally, the catalyst showed high recyclability up to 10 times without loss of activity or palladium leaching.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Hector Fernandez-Perez, Pawel Lenartowicz, Lucas Carreras, Arnald Grabulosa, Pawel Kafarski, Anton Vidal-Ferran
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Inorganic & Nuclear
Javier C. Cordoba, Anton Vidal-Ferran, Merce Font-Bardia, Arnald Grabulosa
Article
Chemistry, Multidisciplinary
Juanjo Cabezas-Gimenez, Vanesa Lillo, Jose Luis Nunez-Rico, M. Nieves Corella-Ochoa, Jesus Jover, Jose Ramon Galan-Mascaros, Anton Vidal-Ferran
Summary: TAMOF-1, a homochiral metal-organic framework (MOF) constructed from an amino acid derivative and Cu(II), was investigated as a heterogeneous catalyst in kinetic resolutions involving the ring opening of styrene oxide with a set of anilines. The results showed that TAMOF-1 exhibited potential applications in the reaction of epoxides with anilines, with the capability of maintaining catalytic activity through multiple cycles. Additionally, TAMOF-1 was found to enhance enantioselectivity in the ring opening reaction of styrene oxide and promote the formation of various isomeric products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Carmen Gonzalez-Galan, Mabel de Fez-Febre, Stefano Giancola, Jesu's Gonzalez-Cobos, Anton Vidal-Ferran, Jose Ramon Galan-Mascaros, Salvador R. G. Balestra, Sofia Calero
Summary: TAMOF-1 is a metal-organic framework with high thermal and chemical stability, suitable for separating chiral isomers and organic mixtures. Experimental and simulation results demonstrate its effectiveness in separating volatile organic compounds.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Inorganic & Nuclear
Javier Eusamio, Yaiza M. Medina, Javier C. Cordoba, Anton Vidal-Ferran, Daniel Sainz, Albert Gutierrez, Merce Font-Bardia, Arnald Grabulosa
Summary: Enantiopure P-stereogenic methylphosphane-boranes have been used to prepare organometallic compounds with chiral phosphine ligands. These compounds exhibit good catalytic activity and selectivity in hydrogenation and transfer hydrogenation reactions.
DALTON TRANSACTIONS
(2023)
Article
Nanoscience & Nanotechnology
Jose Luis Nunez-Rico, Juanjo Cabezas-Gimenez, Vanesa Lillo, Salvador R. G. Balestra, Jose Ramoon Galan-Mascaros, Sofia Calero, Anton Vidal-Ferran
Summary: Metal-organic frameworks (MOFs) with tunable properties and controlled dimensionality have shown promising potential for various applications. The incorporation of chirality into MOFs opens up new strategies for chiral separation, which is crucial in the pharmaceutical industry. In this study, computational modeling and experiments were combined to demonstrate the efficiency, versatility, robustness, and reusability of TAMOF-1-packed HPLC columns as the chiral stationary phase. The in silico studies predicted plausible separations of chiral compounds from different families, and the experimental results confirmed the validity of the models and the high performance of TAMOF-1 columns. The use of in silico screening in chiral chromatography is an unprecedented achievement.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Alba Martinez-Bascunana, Jose Luis Nunez-Rico, Lucas Carreras, Anton Vidal-Ferran
Summary: The choice of counterion has a significant impact on metal-catalyzed reactions, as it can modify the performance of the catalyst and influence the reaction rate and selectivity. In this study, the effects of counterion variation in cationic halogen bond-assembled Rh(I) catalysts in the hydroboration reaction of terminal alkynes were investigated. It was found that higher coordination ability of the counterion led to higher activity and selectivity towards hydroboration products, which was demonstrated through catalytic and spectroscopic studies. The practicality of the synthetic method was demonstrated by developing one-pot hydroboration/Csp2-Csp2 coupling processes.
Article
Chemistry, Physical
Alicia Martinez-Carrion, Andres Romero-Navarro, Jose Luis Nunez-Rico, Albert Gutierrez, Arnald Grabulosa, Anton Vidal-Ferran
Summary: Active catalysts derived from cobalt and the Xantphos ligand were synthesized and tested in the hydroformylation of pure linear alkenes or their mixtures. The catalyst showed good reactivity and selectivity, converting linear alkenes into linear aldehydes with consistent regioselectivity regardless of the starting materials' position or geometry of the C=C double bond. Additionally, this chemistry proved to be an interesting strategy for valorizing mixtures of linear alkenes, producing a major aldehyde while limiting the formation of by-products.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Lijuan Han, Jesus Gonzalez-Cobos, Irene Sanchez-Molina, Stefano Giancola, Scott J. Folkman, S. Gimenez, A. Vidal-Ferran, Jose Ramon Galan-Mascaros
SUSTAINABLE ENERGY & FUELS
(2020)
Article
Chemistry, Organic
Lucas Carreras, Antonio Franconetti, Arnald Grabulosa, Antonio Frontera, Anton Vidal-Ferran
ORGANIC CHEMISTRY FRONTIERS
(2020)
Article
Chemistry, Multidisciplinary
Ester Iniesta, Anton Vidal-Ferran
CHEMICAL COMMUNICATIONS
(2020)
