Article
Chemistry, Multidisciplinary
Kristina Plevova, Peter Kisszekelyi, Denisa Vargova, Samuel Andrejcak, Viktor Toth, LukaS Fertal, Erik Rakovsky, Juraj Filo, Radovan Sebesta
Summary: This study demonstrates the diastereoselective double C-H heteroarylation of chiral ferrocenes using Pd-complexes with chiral mono-protected amino acids, resulting in a variety of functionalized compounds. The absolute configurations of CH-activation products were confirmed using X-ray crystallographic analysis and CD spectroscopy, while insights into the reaction mechanism and stereoinduction were provided by F-19 NMR kinetic study and DFT calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Xin-Meng Chen, Ling Zhu, Dian-Feng Chen, Liu-Zhu Gong
Summary: The chiral indoline-2-carboxylic acid enables a highly enantioselective Catellani-type annulation, directly assembling a diverse range of chiral all-carbon bridged ring systems with high levels of stereochemical control through coordinating orientation to the arylpalladium(II) center identified by control experiments and DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ye Lin, Tristan von Muenchow, Lutz Ackermann
Summary: 3D metallaelectro-catalyzed C-H activation is a promising strategy to obtain valuable organic molecules in an economically and environmentally friendly manner. However, achieving enantioselective C-H activation using 3D metals is challenging and has limited progress. In this study, we combined cobaltaelectro-catalyzed C-H activation with asymmetric catalysis to achieve highly enantioselective annulation of allenes, resulting in a wide range of chiral compounds with good yields and high enantioselectivities. This approach demonstrated practicality by diversifying complex bioactive compounds and drug molecules, as well as conducting large-scale enantioselective electrocatalysis in continuous flow.
Article
Chemistry, Organic
Ayumi Inami, Yuji Nishii, Koji Hirano, Masahiro Miura
Summary: In this study, a new synthetic method was developed using vinyl selenone as a surrogate for phenylacetylene in the Rh-catalyzed annulative coupling reaction. This method successfully produced 3,4-nonsubstituted isoquinoline compounds. The reaction conditions were mild and the vinyl selenone could be recovered and recycled.
Article
Chemistry, Physical
Pablo Vazquez-Dominguez, Antonio Romero-Arenas, Rosario Fernandez, Jose Maria Lassaletta, Abel Ros
Summary: The catalytic hydroarylation of alkynes is a useful method for synthesizing functionalized alkenes with excellent control of regio- and stereochemistry. However, there is a scarcity of asymmetric methodologies in this field. In this study, an atroposelective Ir-catalyzed C-H hydroarylation of alkynes was developed, enabling the asymmetric synthesis of axially chiral heterobiaryl trisubstituted olefins with high yields and enantioselectivities up to 98% ee.
Article
Chemistry, Multidisciplinary
Lu-Lu Han, Yu-Ming Cui, Qin Yang, Li-Lei Fang, Li-Wen Xu
Summary: Palladium-catalyzed asymmetric C-H functionalization and Heck reactions are important strategies for synthesizing quaternary stereocenters. However, developing enantioselective Pd-II-catalyzed cascade reactions remains challenging. In this study, an unprecedented [3+2] annulation of oxime ethers and alkynes was developed, providing spiro and nonspiro indenes with all-carbon quaternary stereocenters in high yields and excellent enantioselectivities. This annulation was achieved by combining atroposelective C-H activation/double carbopalladation and transient axial-to-central chirality transfer, representing a successful catalytic chirality transfer strategy involving axially chiral styrene intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
David Savary, Olivier Baudoin
Summary: C-H activation-based ring-forming methods are powerful for constructing complex molecular structures, especially useful for synthesizing chiral polycyclic aromatic hydrocarbons and other important organic electronic materials. A new enantioselective synthesis method using Pd-catalyzed C(sp(2))-H arylation protocol has been described, delivering diverse polycyclic compounds with high yield and good to excellent enantioselectivity, with investigation into their chiroptical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Romain Melot, Marco Zuccarello, Diana Cavalli, Nadja Niggli, Michael Devereux, Thomas Burgi, Olivier Baudoin
Summary: This study showcases the unique reactivity profile of the IBiox ligand family in the Pd-0-catalyzed functionalization of nonactivated enantiotopic secondary C-H bonds, demonstrating high enantioselectivities for a broad range of valuable indane products. Analysis of the steric maps of the IBiox ligands provides insights into the correlation between enantioselectivity and spatial quadrants occupancy, offering a blueprint for designing more efficient ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kai Wang, Xiangfeng Lin, Yan Liu, Can Li
Summary: This study presents a novel catalytic asymmetric [4+2] cycloaddition reaction, achieved through direct allylic C-H functionalization with high diastereoselectivities and enantioselectivities to synthesize hydroquinolines.
Article
Chemistry, Organic
Zengyin Chao, Na Li, Biqiong Hong, Mingming Ma, Zhenhua Gu
Summary: A palladium-catalyzed ring-opening reaction of optically active ferrocenyl tertiary alcohols for the construction of planar chiral ketones was reported. The stereochemistry of the hydroxyl group in ferrocenyl alcohols significantly affects the reaction, with beta-hydroxyl group showing better reactivity and chemoselectivity. Treatment of alpha-hydroxyl substrates with trifluoroacetic acid successfully enables the inversion of the hydroxyl group orientation to the corresponding beta-analogues.
Article
Chemistry, Physical
Raju S. Thombal, Peter Yuosef M. Rubio, Daesung Lee, Debabrata Maiti, Yong Rok Lee
Summary: Metal catalyzed cascade C-H activation/annulation is a highly promising approach for the construction of aromatic and heteroaromatic compounds. Pd-complexes play a crucial role in this method, enabling high catalytic efficiency through the activation of molecules bearing a directing group.
Article
Chemistry, Multidisciplinary
Xiaoqiang Yan, Jijun Jiang, Jun Wang
Summary: In this study, an unusual class of planar-chiral rhodium catalysts bearing non-chiral Cp ligands was described. These catalysts are readily tunable and were successfully used in enantioselective C-H activation reactions, showing great potential in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bo Yang, Jihui Gao, Xingfa Tan, Yicong Ge, Chuan He
Summary: A new type of chiral silyl ligand is developed, enabling the first iridium-catalyzed atroposelective intermolecular C-H silylation reaction of 2-arylisoquinolines. This protocol offers mild reaction conditions, high atom economy, and remarkable yield with excellent stereoselectivity, delivering enantioenriched axially chiral silane platform molecules with facile convertibility. The success of this unprecedented transformation relies on a novel chiral PSiSi-ligand, which facilitates the intermolecular C-H silylation process with perfect chem-, regio-, and stereo-control via a multi-coordinated silyl iridium complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ziyang Dong, Jia Li, Ting Yao, Changgui Zhao
Summary: Planar-chiral cyclophanes have attracted increasing attention in drug discovery and catalyst design. This paper describes the first Pd(II)-catalyzed enantioselective C-H olefination of prochiral cyclophanes. The reaction proceeds through dynamic kinetic resolution, providing high yields and excellent enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qiyuan He, Naoto Chatani
Summary: The palladium-catalyzed [3+2] annulation of aromatic amides with maleimides via the activation of ortho benzylic C-H and meta C-H bonds is reported, with a key role played by the presence of a 2-methylthiophenyl directing group for the success of the reaction. The irreversible cleavage of these C-H bonds leads to the formation of five-membered cyclic products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
