Article
Chemistry, Organic
Jianfei Yu, Haowei Zhu, Xumu Zhang, Gen-Qiang Chen
Summary: A new series of chiral ferrocene-based diphosphino-ethane ligands, f-DPE, were developed and applied in the hydrogenation of 2-substituted acrylic acids to obtain chiral propanoic acids with high yields and enantioselectivities. The synthesis of well-known anti-inflammatory drugs, such as ibuprofen, naproxen, and flurbiprofen, was also efficiently achieved using this method. The synthetic utilities of the method were demonstrated through gram-scale experiments.
Article
Chemistry, Physical
Lixian Wang, Jin Lin, Qiangsheng Sun, Chungu Xia, Wei Sun
Summary: A series of Mn(I) catalysts with chiral bidentate benzimidazoles derived from easily available amino acids have been developed for asymmetric transfer hydrogenation (ATH), showing high activity and enantioselectivity. These phosphine-free chiral Mn catalysts can efficiently convert bulky substrates into drug intermediate alcohols, with a possible mechanism and enantiocontrol model proposed based on experimental and DFT studies.
Article
Chemistry, Multidisciplinary
Matthias Peeters, Jonathan Decaens, Alois Fuerstner
Summary: Chiral [BiRh]-paddlewheel complexes empowered by London dispersion enable the generation of (trifluoromethyl)furfurylidene metal complexes from a bench-stable triftosylhydrazone precursor. These complexes undergo asymmetric [2+1] cycloadditions, providing optically active trifluoromethylated cyclopropane or -cyclopropene derivatives, which are important building blocks for medicinal chemistry and difficult to obtain in optically active form.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuki Saito, Shu Kobayashi
Summary: The application of heterogeneous catalysts in continuous-flow enantioselective hydroacylation reactions was studied. Catalysts were prepared by mixing supports and rhodium complexes, and showed excellent activity and enantioselectivity. Under optimized conditions, the catalysts exhibited high turnover numbers and could be applied to various substrates. Furthermore, sequential-flow reactions with other heterogeneous catalysts were demonstrated for the synthesis of biologically active molecules and functional materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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)
Review
Chemistry, Organic
Fang Zhao, Wenjing Ye, Kai Wang
Summary: The study of chiral monophosphorous ligands, especially chiral mono-phosphites ligands and mono-phosphoramidites ligands, has attracted widespread attention since the 21st century. These ligands are widely used in various asymmetric catalytic reactions for their ease of synthesis and excellent stability, activity, and enantioselectivity. The diverse common monodentate phosphonites, phosphites, and phosphoramidites ligands and their applications in asymmetric hydrogenations have made significant progress over the past two decades.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Daisuke Sakamoto, Isabel Gay Sanchez, Jiri Rybacek, Jaroslav Vacek, Lucie Bednarova, Marketa Pazderkova, Radek Pohl, Ivana Cisarova, Irena G. Stara, Ivo Stary
Summary: This study describes an asymmetric synthesis method for the preparation of optically pure and conformationally locked oxabenzo[5]helicenes. These compounds can be transformed into cycloiridated organometallics and exhibit excellent catalytic performance in asymmetric transfer hydrogenation reactions.
Article
Chemistry, Multidisciplinary
Fan Wang, Shuai Zhang, Sen Huang, Lin Zhu, Hongbing Song, Congxia Xie, Xin Jin
Summary: A novel class of room temperature chiral phosphine-functionalized polyether imidazolium ionic liquids (RTCP-PolyIMILs) was synthesized for the first time by an ion exchange reaction. The resulting RTCP-PolyIMILs showed attractive dual functionalities as a phosphine ligand and a carrier in a sustainable homogeneous catalysis and biphasic separation system (HCBS) for Ru(ii)-catalyzed enantioselective hydrogenation. The RTCP-PolyIMIL catalyst exhibited higher activity, better adaptability, long-term stability, and good enantioselectivity, compared to the traditional Ru(ii)-BINAP catalyst.
Article
Chemistry, Multidisciplinary
Kyzgaldak Ramazanova, Soumyadeep Chakrabortty, Bernd H. Mueller, Peter Loennecke, Johannes G. de Vries, Evamarie Hey-Hawkins
Summary: A convenient synthesis method for enantiopure mixed donor phosphine-phosphite ligands has been developed, incorporating P-stereogenic phosphanorbornane and axially chiral bisnaphthols into one ligand structure. These ligands exhibited excellent selectivity and moderate enantioselectivity in various catalyzed reactions.
Article
Chemistry, Organic
Luca Vaghi, Roberto Cirilli, Marco Pierini, Simona Rizzo, Giancarlo Terraneo, Tiziana Benincori
Summary: PHANE-TetraPHOS, a novel D-2 symmetric tetraphosphane, features four homotopic diphenylphosphane groups with indistinguishable spatial arrangement. Enantiomeric purity was achieved through crystallization and alkaline treatment, leading to enantiopure PHANE-TetraPHOS antipodes. These ligands showed comparable catalytic activity and enantiodiscrimination ability to PHANEPHOS, using only half the amount of chiral ligand.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yunnan Xu, Delong Liu, Yu Deng, Yi Zhou, Wanbin Zhang
Summary: An asymmetric hydrogenation of 3-benzoylaminocoumarins was achieved for the first time using the BridgePhos-Rh catalytic system, providing chiral 3-amino dihydrocoumarins in high yields and with excellent enantioselectivities. The relationship between the enantioselectivities of the hydrogenations and the dihedral angles and the resulting pi-pi stacking effects of the BridgePhos-Rh complexes, determined by X-ray diffraction analysis, was discussed. The corresponding hydrogenated products allow for many transformations, providing several chiral skeletons with important physiological and pharmacological activities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Xue-Song Gu, Ying Xiong, Fan Yang, Na Yu, Pu-Cha Yan, Jian-Hua Xie, Qi-Lin Zhou
Summary: An iridium-catalyzed asymmetric hydrogenation method involving dynamic kinetic resolution was successfully developed using chiral spiro PNN-ligands containing a C5-substituted chiral oxazoline unit. This protocol, combined with simple dehydration, provides a straightforward approach to prepare enantiomerically enriched 3-aryloxy tetrahydrofurans, which are prevalent structural motifs in many approved drugs and clinical candidates.
Article
Chemistry, Multidisciplinary
Junqiang Wei, Vincent Gandon, Ye Zhu
Summary: Synthetic application of asymmetric catalysis requires strategic alignment of bond construction and chiral target molecule creation. Remote desymmetrization offers advantages in spatial decoupling of catalytic transformation and generation of stereogenic element. However, this spatial separation presents challenges for chiral catalysts to discriminate distant enantiotopic sites several bonds away from a prochirality center.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiangqing Feng, Wei Meng, Haifeng Du
Summary: Olefins are easily accessible compounds that have dual functions as popular substrates in synthetic chemistry and ligands in organometallic complexes. This study provides a summary of the development of chiral diene ligands and chiral FLP catalysts for asymmetric catalysis. The results show that these ligands and catalysts are highly effective in various asymmetric reactions.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Roman A. Pototskiy, Mikhail A. Boym, Yulia Nelyubina, Dmitry S. Perekalin
Summary: A novel ruthenium complex with a chiral arene ligand was synthesized and used for the asymmetric hydrogenation of acetophenone. However, the complex decomposed in catalytic reactions involving C-H activation of 2-phenylpyridine or benzoic acid derivatives.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Jose Luis Nunez-Rico, Marcos Rellan-Pineiro, Begona Puertolas, Anton Vidal-Ferran, Nuria Lopez, Javier Perez-Ramirez, Stefan Wershofen
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Hector Fernandez-Perez, Joan R. Lao, Arnald Grabulosa, Anton Vidal-Ferran
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
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)
