Article
Chemistry, Multidisciplinary
Linxi Yao, Alemayehu Gashaw Woldegiorgis, Shaoying Huang, Yongtao Wang, Xufeng Lin
Summary: We report a highly enantioselective desymmetrization reaction for the synthesis of axially chiral biaryl N-oxides by atroposelective C-H iodination using a chiral catalyst coordinated by N-benzoyl-l-phenylalanine. A broad range of products were obtained in high yields (up to 99%) with excellent enantioselectivities (up to 98% ee). The products could be synthesized in gram scale, and one of them was shown to be a powerful organocatalyst in asymmetric allylation reaction. Mechanistic evidence and DFT calculations provide insights into the factors leading to high reactivity and excellent enantiocontrol in this reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ziyong Li, Ying Chen, Chuang Wang, Guangyang Xu, Ying Shao, Xinhao Zhang, Shengbiao Tang, Jiangtao Sun
Summary: The atroposelective synthesis of biaryl atropisomers via asymmetric C(sp(2))-H bond insertion reaction of arenes under rhodium catalysis has been achieved, providing moderate to excellent yields with good enantiomeric ratios. Further investigation suggests that this type of axially biaryl scaffold may have promising potentials in developing novel chiral ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Si-Yong Yin, Qiansujia Zhou, Chen-Xu Liu, Qing Gu, Shu-Li You
Summary: The iridium-catalyzed asymmetric C-H alkylation was used for the first time to construct N-N biaryl atropisomers. The method showed good yields (up to 98%) and excellent enantioselectivity (up to 99% ee) for the synthesis of axially chiral molecules based on indole-pyrrole skeleton. This method also allowed the synthesis of N-N bispyrrole atropisomers with high yields and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, 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, Applied
Zuo-Yu Zhang, Bo-Bo Gou, Quannan Wang, Qing Gu, Shu-Li You
Summary: A Rh-catalyzed asymmetric C(sp(3))-H arylation of 8-benzylquinolines with arylboronic acids has been developed. The reaction proceeds smoothly with good to excellent enantioselective control, giving a series of enantioenriched triarylmethanes in moderate to good yields (24-89% yields, 63-93% ee). This method shows a broad substrate scope and good functional group tolerance under mild conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin
Summary: In this study, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines was developed, leading to the synthesis of aminophosphinites and P-chiral aminophosphinites. The reaction mechanism was proposed and further transformation to P-chiral phosphines was achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhi-Jie Wu, Zhuo Wu, Wen-Wen Zhang, Qing Gu, Shu-Li You
Summary: This study reports the Rh(III)-catalyzed highly enantioselective intermolecular C-H addition of aryl oxime ethers to glyoxylates. The method achieves excellent yields and enantioselectivity under mild conditions. It not only expands the C-H addition approach but also provides a proof of concept for developing broader asymmetric C-H addition reactions.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Wen-Wen Zhang, Qiang Wang, Su-Zhen Zhang, Chao Zheng, Shu-Li You
Summary: Satoh-Miura reaction is an important method for extending pi-systems via C-H activation and alkynyl annulation. However, achieving high enantioselectivity remains challenging. In this study, an asymmetric Satoh-Miura reaction using a SCpRh-catalyst is reported, and it is found that choosing the counteranion of the catalyst is crucial for the desired reactivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Jose A. Carmona, Patricia Rodriguez-Salamanca, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes is achieved by transfer hydrogenative coupling of allyl acetate. The reaction leads to the installation of central and axial chirality, with high diastereoselectivities and excellent enantioselectivities when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates is facilitated through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jose A. Carmona, Carlos Rodriguez-Franco, Joaquin Lopez-Serrano, Abel Ros, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An efficient dynamic kinetic resolution (DKR) approach has been developed for the synthesis of axially chiral diamines based on ruthenium-catalyzed enantioselective transfer hydrogenation. This method features a broad substrate scope and proceeds under very mild conditions, allowing the preparation of BINAM homologues in good to high yields and nearly perfect enantioselectivities (up to 99% ee).
Review
Chemistry, Organic
Helene Pellissier
Summary: Enantioselective indium-catalyzed transformations have become a promising research field, offering the potential to replace toxic metals with greener processes in the near future.
SYNTHESIS-STUTTGART
(2021)
Article
Biochemistry & Molecular Biology
Aiqi Xue, Xingfu Wei, Yue Huang, Jingping Qu, Baomin Wang
Summary: In this work, the stereoselective union of a point chiral center with allenyl axial chirality in the 1,3-position was achieved through Pd-catalyzed asymmetric allenylic alkylation. The reaction showed high yields (up to 99%), excellent enantioselectivities (up to 98% ee), and good diastereoselectivities (up to 13:1 dr) for various functional groups.
Review
Chemistry, Inorganic & Nuclear
Helene Pellissier
Summary: This review summarizes the recent advances in enantioselective zinc-catalyzed transformations since the beginning of 2015, highlighting the development of a range of highly enantioselective reactions in the past six years.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Jia-Hao Xie, Yi-Ming Hou, Zuolijun Feng, Shu-Li You
Summary: Here, we describe a synthesis method for cyclohexanones with multiple continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium-catalyzed asymmetric allylic substitution reaction. The reaction yields good to excellent results in terms of yield, diastereoselectivity, and enantioselectivity. Unlike previous studies focusing on adjacent stereocenter construction (1,2-position), this reaction achieves stereodivergent construction of nonadjacent stereocenters (1,3-position) by utilizing two chiral catalysts with different enantiomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Wen-Wen Zhang, Qiang Wang, Su-Zhen Zhang, Chao Zheng, Shu-Li You
Summary: Satoh-Miura reaction is an important method for extending pi-systems via C-H activation and alkynyl annulation. However, achieving high enantioselectivity remains challenging. In this study, an asymmetric Satoh-Miura reaction using a SCpRh-catalyst is reported, and it is found that choosing the counteranion of the catalyst is crucial for the desired reactivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Si-Yong Yin, Qiansujia Zhou, Chen-Xu Liu, Qing Gu, Shu-Li You
Summary: The iridium-catalyzed asymmetric C-H alkylation was used for the first time to construct N-N biaryl atropisomers. The method showed good yields (up to 98%) and excellent enantioselectivity (up to 99% ee) for the synthesis of axially chiral molecules based on indole-pyrrole skeleton. This method also allowed the synthesis of N-N bispyrrole atropisomers with high yields and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Wen-Yun Zhang, Hu-Chong Wang, Ye Wang, Chao Zheng, Shu-Li You
Summary: This study describes an enantioselective dearomatization of indoles via SmI2-mediated intermolecular reductive coupling with ketones. The utilization of samarium reductant supported by chiral tridentate aminodiol ligands allows the facile synthesis of indoline molecules bearing two contiguous stereogenic centers in high yields and stereoselectivity. Experimental and computational investigations suggest that parallel single-electron transfer to each substrate from the chiral samarium reductant enables enantioselective radical-radical recombination, which is a unique mechanistic scenario in SmI2-mediated reductive coupling reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xian-Yun Huang, Pei-Pei Xie, Lei-Ming Zou, Chao Zheng, Shu-Li You
Summary: Here, we report a highly efficient synthesis method for enantioenriched aza-[3.3.1]-bicyclic enamines and ketones using indoles and azodicarboxylates through asymmetric dearomatization. The reaction involves electrophilic amination followed by aza-Prins cyclization/phenonium-like rearrangement. A newly developed fluorine-containing chiral phosphoric acid catalyst shows excellent activity in promoting this cascade reaction. The presence or absence of water directs the reaction towards enamine or ketone products, with high yields (up to 93%) and enantiopurity (up to 98% ee). DFT calculations reveal the energy profile, enantioselectivity, and water-induced chemoselectivity of the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chao Zheng, Shu-Li You, Chen-Xu Liu, Pei-Pei Xie, Fangnuo Zhao, Quannan Wang, Zuolijun Feng, Haoyang Wang
Summary: Through comprehensive experimental and computational studies, the mechanism of Rh(I)-catalyzed C-H arylation has been elucidated, including the identification of each elementary step in the catalytic cycle and the structural characterization of key intermediates and transition states. This research provides a foundation for the rational design and development of challenging intramolecular reactions and successfully realizes the facile synthesis of planar chiral [m]ferrocenophanes, a class of rarely explored target molecules with strained structures and intriguing molecular topology.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Yang Zheng, Wen-Yun Zhang, Qing Gu, Chao Zheng, Shu-Li You
Summary: In this study, a cobalt(III)-catalyzed asymmetric ring-opening reaction of 7-oxabenzonorbornadienes was reported, which achieved high yields and excellent enantioselectivity for the target products. Experimental and computational studies revealed that the selectivity-determining step of the reaction is beta-oxygen elimination.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Hui Yang, Ru Zhang, Su-Zhen Zhang, Qing Gu, Shu-Li You
Summary: Researchers have developed a series of chiral spiro ligands (BCSCp) from commercially available and cheap Bisphenol C, and prepared their corresponding rhodium complexes. These complexes have been successfully applied in enantioselective aryl C-H addition to nitroalkenes, producing C-H adducts with yields up to 88% and ee up to 98%.
Review
Chemistry, Multidisciplinary
Chen-Xu Liu, Si-Yong Yin, Fangnuo Zhao, Hui Yang, Zuolijun Feng, Qing Gu, Shu-Li You
Summary: This review summarizes the advancements in rhodium-catalyzed asymmetric C-H functionalization reactions during the last two decades. It has attracted extensive attention due to its unique reactivity and selectivity parallel to the rapidly developed palladium catalysis. In recent years, significant developments have been made in catalyst design, reaction development, mechanistic investigation, and application in the synthesis of complex functional molecules. This review provides an explicit outline of catalysts and ligands, mechanism, the scope of coupling reagents, and applications.
Article
Chemistry, Multidisciplinary
Pusu Yang, Rui-Xiang Wang, Xu-Lun Huang, Yuan-Zheng Cheng, Shu-Li You
Summary: Here, we report an efficient synthetic method for enantioenriched cyclobutane derivatives, which involves Ir-catalyzed asymmetric allylic etherification and visible-light induced [2 + 2] cycloaddition. This method provides a diverse range of chiral cyclobutanes with excellent yields and high enantioselectivities under mild reaction conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qing-Xia Zhang, Jia-Hao Xie, Qing Gu, Shu-Li You
Summary: An asymmetric allylic dearomatization reaction of 1-nitro-2-naphthol derivatives with Morita-Baylis-Hillman (MBH) adducts has been developed using a Pd catalyst and Trost ligand (R,R)-L1. The reaction proceeds smoothly in 1,4-dioxane at room temperature, resulting in good yields (up to 92%) and enantioselectivity (up to 90% ee) of substituted beta-naphthalenones. Various substituted 1-nitro-2-naphthols and MBH adducts are compatible under the optimized conditions. This reaction provides a convenient method for the synthesis of enantioenriched 1-nitro-beta-naphthalenone derivatives.
CHEMICAL COMMUNICATIONS
(2023)
