Review
Chemistry, Inorganic & Nuclear
Jessica Margalef, Maria Biosca, Pol de la Cruz Sanchez, Jorge Faiges, Oscar Pamies, Montserrat Dieguez
Summary: The success of phosphine-oxazoline ligands has led to advancements in P-oxazoline ligand families, resulting in diverse structures and more efficient ligands for asymmetric transformations. Through proper design, these heterodonor bidentate ligand families exhibit superior catalytic performance in a variety of asymmetric reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Conor L. Oates, Alister S. Goodfellow, Michael Buhl, Matthew L. Clarke
Summary: DFT calculations were carried out on the full catalytic cycle of manganese catalysed enantioselective hydrogenation of a selection of ketones. It was found that Mn complexes with a chiral P,N,N ligand showed the highest reactivity in a facial coordination mode. The use of a new ligand transformed the levels of enantioselectivity for the hydrogenation of cyclic ketones. In silico evaluation of substrates accurately predicted experimental results.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Lin Liu, Kai-Xin Guo, Yu Tian, Chang-Jiang Yang, Qiang-Shuai Gu, Zhong-Liang Li, Liu Ye, Xin-Yuan Liu
Summary: The copper-catalyzed asymmetric cross-coupling of C(sp(3))-C(sp) bonds with terminal alkynes reported in this study shows high to excellent enantioselectivity. The rational design of chiral oxazoline-derived ligands is critical for success in tolerating oxidative conditions and inducing challenging enantiocontrol. This approach offers direct access to a variety of synthetically useful compounds and has great potential for the synthesis of enantioenriched medicinally relevant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yu-Qing Bai, Xin-Wei Wang, Bo Wu, Xiao-Qing Wang, Rong-Zheng Liao, Man Li, Yong-Gui Zhou
Summary: The development of chiral ligands for precise stereocontrol is essential in asymmetric catalysis. However, the utilization of chiral oxazole-pyridine-type ligands has been limited compared to established chiral pyridine-pyridine and pyridine-oxazoline-type ligands. In this study, a new class of planar-chiral oxazole-pyridine N,N-ligands based on [2.2]paracyclophane was designed and synthesized. These ligands exhibited excellent performance in the enantioselective palladium-catalyzed acetoxylative cyclization, providing chiral cis-hydrobenzofurans with potent NF-κB inhibition, thereby demonstrating the promising potential of chiral oxazole-pyridine ligands as an efficient N,N-ligand scaffold.
Article
Chemistry, Multidisciplinary
Tino P. Golub, Ayham H. Abazid, Boris J. Nachtsheim, Christian Merten
Summary: In this study, vibrational circular dichroism (VCD) spectroscopy was used as an experimental technique to verify DFT-calculated chiral iodane structures. The research revealed that an undescribed cationic chiral iodane was the most common intermediate under oxidative conditions, with significant intramolecular interactions and no significant interactions with potential anionic ligands. Aggregation of the substrates resulted in the formation of a non-coordinating anionic hydrogen bonded complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Andrea Daru, Carlos Martin-Fernandez, Jeremy N. Harvey
Summary: This article presents a mechanistic investigation of the iron-catalyzed Kumada reaction involving clusters as active species. It suggests that 11- and 13-coordinated clusters are fundamental for initiating the reaction, and proposes a classic initiation step.
Article
Chemistry, Multidisciplinary
Manuel Weh, Asja A. Kroeger, Kazutaka Shoyama, Matthias Gruene, Amir Karton, Frank Wuerthner
Summary: Enzymes catalyze reactions through transition state stabilization and ground state destabilization, achieving enantioselectivity with chiral binding sites. This study presents a supramolecular model system that uses these principles to catalyze the enantiomerization of [5]helicene. The catalysis is mediated by p-p catalysis from a curved aromatic framework of a chiral perylene bisimide (PBI) cyclophane, which offers a binding pocket complementary to the enantiomerization transition structure. The catalytic effect is lost when the configurational inversion occurs in one PBI moiety, emphasizing the importance of precise recognition of transition structure in supramolecular enzyme mimics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zi-Chao Wang, Pei-Pei Xie, Youjun Xu, Xin Hong, Shi-Liang Shi
Summary: The use of a bulky yet flexible chiral N-heterocyclic carbene (NHC) ligand in low-temperature Ni-catalyzed C-N cross-coupling has achieved high enantioselectivity with low barriers. Computational studies show that the rotations of multiple sigma-bonds on the chiral ligand can adapt to the changing needs of catalytic processes, making this design widely applicable to diverse transition states for challenging metal-catalyzed asymmetric cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Kai-Cheng Yu, Hai Li, Yuan-Hong Tu, Hui Zhao, Xiang-Guo Hu
Summary: We have developed a non-toxic and non-corrosive dual copper/photoredox-catalyzed method for the synthesis of P(O)-N bond from commercially available compounds. This method has a broad substrate scope and is suitable for the direct modification of drug molecules.
Article
Chemistry, Inorganic & Nuclear
Sanjay Gaire, Briana R. Schrage, Christopher J. Ziegler
Summary: It has been shown that an organometallic complex mimicking an amino acid can be synthesized, and by adjusting the structure of the metal species, compounds with different chirality can be produced.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ziqian Bai, Fangfang Song, Hao Wang, Wangxing Cheng, Shiyang Zhu, Yi Huang, Gang He, Gong Chen
Summary: P-N and P=N bonds are crucial in the design and synthesis of functional molecules. This paper presents a nitrene-mediated intermolecular P-N coupling reaction, offering a simple and versatile method for the synthesis of various N-P compounds from different phosphorus nucleophiles and dioxazolones.
Article
Chemistry, Multidisciplinary
Mei-Ling Tan, M. Angeles Gutierrez Lopez, Naomi Sakai, Stefan Matile
Summary: This article introduces the principles and applications of anion-pi catalysis and anion-(pi)(n)-pi catalysis. The self-assembly of micelles is utilized to achieve anion-(pi)(n)-pi catalytic reactions in water, with high reaction rates and autocatalytic behavior.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mei-Ling Tan, M. Angeles Gutierrez Lopez, Naomi Sakai, Stefan Matile
Summary: Anion-pi catalysis operates by stabilizing anionic transition states on pi-acidic aromatic surfaces. In this study, amphiphilic naphthalenediimides (NDIs) were self-assembled into micelles, and charge-transfer complexes with dialkoxynaphthalenes (DANs) were installed to interface substrates and catalysts. By adjusting the pi acidity of the micelles, the rate of catalytic reactions can be enhanced.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Jaehan Bae, Eun Jin Cho
Summary: Bidentate P,N ligands, integrating phosphine and nitrogen donors, have versatile characteristics and offer electronic and steric tunability. This Review focuses on Ni-catalyzed cross-coupling reactions mediated by P,N ligands, with their asymmetrical nature playing a crucial role in the catalytic cycle and providing control, stability, and unique regioselectivity in catalytic processes.
Article
Chemistry, Applied
Yasuaki Fukazawa, Vladimir Yu. Vaganov, Julia V. Burykina, Artem N. Fakhrutdinov, Ruslan I. Safiullin, Felix Plasser, Aleksandr E. Rubtsov, Valentine P. Ananikov, Andrei V. Malkov
Summary: The mechanism of metal-catalyzed asymmetric alkylation of indoles remains uncertain. In this study, the authors investigate the mechanism from both molecular and nano-level perspectives, revealing the role of water and catalyst precursor on reaction selectivity and performance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)