Article
Chemistry, Multidisciplinary
Li Ling, Zeli Song, He Shan, Chao Wang, Shouting Li, Yanjiao Wang, Jianfeng Hu, Qian Chen, Hao Zhang, Yong Yang
Summary: A series of planar chiral indene-fused ferrocenes were successfully synthesized with excellent yields (up to 99%) and high enantioselectivities (up to 99% ee) through intramolecular asymmetric C-H arylation. These compounds were then transformed to chiral ferrocenyl phosphines, featuring both planar and central chiralities, in good yields (up to 83%) and excellent diastereoselectivities (up to 99% de) through diastereoselective phosphination. The newly developed ligands demonstrated potential applications in a Pd-catalyzed enantioselective allylic alkylation reaction with high enantioselectivity (92% ee) and good yield (89%).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Ulysse Caniparoli, Imma Escofet, Antonio M. Echavarren
Summary: Planar chiral monodentate 1,3-disubstituted ferrocene phosphines inspired by JohnPhos-type ligands have been synthesized and applied for the enantioselective gold(I) catalyzed [4 + 2] cycloaddition of 1,6-arylenynes. Computational studies elucidated the working mode of the catalyst, involving attractive noncovalent interactions that induce the folding of the substrate in the chiral environment of the ligand.
Article
Chemistry, Multidisciplinary
Ming Cui, Zhi-Yuan Zhao, Martin Oestreich
Summary: Chiral bis(phosphine) monooxides derived from C-2-symmetric bis(phosphines) have been found to exhibit superior enantioselection in copper-catalyzed conjugate borylation and 1,6-addition reactions. Specifically, (R,R)-Bozphos ligand shows significantly higher enantiomeric excesses and chemical yields compared to parent (R,R)-Me-Duphos ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Multidisciplinary Sciences
Shu-Wen Li, Li-Cheng Xu, Cheng Zhang, Shuo-Qing Zhang, Xin Hong
Summary: We report a knowledge-based graph model that embeds digitalized steric and electronic information to achieve predictive modeling of synthetic transformation. A molecular interaction module is developed to learn the synergistic influence of reaction components. The model demonstrates excellent predictions of reaction yield and stereoselectivity, with good extrapolative ability and atomic-level interpretation.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
C. Athira, A. Sreenithya, Christopher M. Hadad, Raghavan B. Sunoj
Summary: The increasing number of examples on cooperative dual catalysis involving organocatalysts and transition metal catalysts indicate their wider acceptance and utility in synthetic applications. In this study, computational investigation using density functional theory reveals the molecular mechanism and energetic features responsible for the high enantio-/diastereoselectivities and cooperativity in dual catalytic reactions.
Article
Chemistry, Multidisciplinary
Chenghao Li, Shu-Xin Zhang, Yu Feng, Yan-Mei He, Qing-Hua Fan
Summary: The chiral ruthenium-catalyzed enantioselective hydrogenation of tetrapyridine-type N-heteroarenes was developed for the first time. The adjacent tetraheteroaromatic substrates showed high reactivity, enantioselectivity, and diastereoselectivity, with yields up to 93%, enantiomeric excess (>99% ee), and diastereomeric ratio of 92:8, respectively, in the presence of phosphine-free chiral cationic ruthenium diamine complexes. The potential application of chiral tetradentate pyridine-amine products as chiral ligands was demonstrated in the Cu-catalyzed asymmetric Friedel-Crafts alkylation reaction between indoles and nitroalkenes.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Organic
Chenga Luo, Yanli Yin, Zhiyong Jiang
Summary: Enantioenriched organophosphates play important roles in chiral ligands, catalysts, and bioactive molecules. Synthetic chemists have made significant efforts to develop efficient methodologies for constructing P-chiral phosphine derivatives, leading to a wide range of chiral organophosphine ligands and promising pharmaceutical molecules. This review summarizes and discusses the progress in the synthesis of P-chiral phosphine oxides from 2020 to 2022, focusing on asymmetric induction, catalytic desymmetrization, catalytic asymmetric synthesis, catalytic kinetic resolution or dynamic kinetic asymmetric transformation, and enzyme catalysis.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhuo-Zhuo Zhang, Lu Jiang, Jun-Long Li, Bing-Feng Shi
Summary: Efficient and stereoselective synthesis of C-ferrocenyl glycosides was achieved through Pd-catalyzed stereoselective C-H glycosylation, providing rapid access to sole bis-C-ferrocenylglycosides in good to high yields (up to 98% yield) with exclusive stereoselectivity. A diverse range of glycosyl chlorides were well tolerated.
Article
Chemistry, Multidisciplinary
Ying Zhang, Jia Yuan, Guanglong Huang, Hong Yu, Jinpeng Liu, Jian Chen, Sixuan Meng, Jian-Ji Zhong, Li Dang, Guang-Ao Yu, Chi-Ming Che
Summary: Visible-light-induced reactions play an important role in organic synthesis, but efficient photochemical synthesis of enantiomerically pure molecules remains a challenge. This study describes a simple and efficient visible-light-induced reaction for the synthesis of P-chiral heteroaryl phosphine oxides.
Article
Chemistry, Organic
Partha Mondal, Rapti Pal, Arun K. Pal, Soumik Das, Anirban Misra, Ayan Datta
Summary: The lack of directionality and long-range nature of Coulomb interactions have hindered chemically precise C-H activation using ion-pairs. However, recent research has shown that ion-pair directed regioselective Ir-catalyzed borylation offers a new direction in utilizing noncovalent interactions for C-H activation. Computational studies reveal that meta C-H activation is more favorable than the para analogue due to stronger electrostatic interactions between ion-pairs in closer proximity. Multiple linear regression and tuned range-separated DFT calculations further elucidate the role of charge density in the activation free energy and the selectivity of the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Karim Muratov, Fabien Gagosz
Summary: In this research, a new class of structurally simple and easily accessible bulky tri-(ortho-biaryl)phosphine ligands and their gold(I) complexes were synthesized. Their confined nature was demonstrated through X-ray diffraction analysis and comparative evaluation. Despite their notable steric congestion, these complexes exhibited remarkable catalytic activities and unusual selectivities, making them unique in the field of synthetic homogeneous gold catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Margaret L. Kelty, Andrew J. McNeece, Josh W. Kurutz, Alexander S. Filatov, John S. Anderson
Summary: This study reports a method to quantify the electrostatic contribution of borate moiety to donor strength using the phosphorus selenium coupling value, and experimentally validates the theoretical predictions regarding electrostatic effects in reactivity. The results demonstrate that covalently bound charged functionalities can significantly influence reactivity under solution phase reaction conditions.
Review
Chemistry, Inorganic & Nuclear
Juan Carlos Perez-Sanchez, Raquel P. Herrera, M. Concepcion Gimeno
Summary: This review explores the recent advancements in the combination of the ferrocene structure with gold-mediated catalysis in the field of organometallic chemistry, discussing the application and potential of ferrocene in gold catalysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Alica C. Keuper, Kevin Fengler, Florian Ostler, Tobias Danelzik, Dariusz G. Piekarski, Olga Garcia Mancheno
Summary: A new approach to achieve highly enantioselective halogen-bonding catalysis has been developed by designing fine-tuned halogen-halogen interactions. This strategy utilizes both the electron cloud and sigma-hole site of the substrate's halogen substituent to form a tight chiral complex, enabling controlled induction of high levels of chirality transfer. Remarkable enantioselectivities of up to 95:5 e.r. (90% ee) have been achieved in a model dearomatization reaction using tetrakis-iodotriazole multidentate anion-binding catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiangjin Kong, Pan-Pan Zhou, Yao Wang
Summary: This study introduces the concept of chalcogen...pi bonding catalysis, which activates molecules of pi systems through interaction between chalcogen and pi-electron cloud. The experimental results demonstrate that S...pi and Se...pi bonding interaction can efficiently drive the cycloaddition reaction, with double Se...pi bonding interaction influencing the stereoselectivity of the process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Runtong Zhang, Xin Yan, Caiyou Chen, Ya-Nan Duan, Xintong He, Shao-Tao Bai, Xumu Zhang
Summary: This paper demonstrates the integration of a Milstein-type Ru-PNN catalyst and a Rh-Tribi/Tetrabi catalyst, resulting in highly improved isomerization linear selective hydroformylation of internal alkenes. The obtained yields exhibit excellent linear selectivities and activities compared to the Ru-PNN/Rh-Bisbi system.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Liangbin Yu, Junjun Liu, Shiyu Xiang, Taotao Lu, Ping Ma, Qingyang Zhao
Summary: By using a chiral silver phosphate catalyst, a direct 5-endo-dig nucleophilic cyclization of 2-alkynylanilins was achieved under mild conditions, leading to the synthesis of various C-C axially chiral 2arylindoles with high yields and enantioselectivities. Control experiments showed the cooperative catalysis of AgOAc and chiral phosphoric acid, with the former accelerating the desired transformation and the latter improving enantioselectivity. Additionally, the synthetic applications and thermal stability of the products were investigated, making it the first example of silver-catalyzed enantioselective de novo synthesis of C-C axially chiral indole skeletons.
Article
Chemistry, Organic
Xiu-Qin Dong, Xuanliang Yang, Gang Liu, Xun Xiang, Dezheng Xie, Jinyu Han, Zhengyu Han
Summary: Efficient Ni/(S,S)-Ph-BPE-catalyzed asymmetric hydrogenation of alpha-substituted alpha,beta-unsaturated phosphine oxides/phosphonates/phosphoric acids has been successfully developed, and a wide range of chiral alpha-substituted phosphine hydrogenation products were obtained in generally high yields with excellent enantioselective control (92%-99% yields, 84%->99% ee). This method features a cheap transition metal nickel catalytic system, high functional group tolerance, wide substrate scope generality, and excellent enantioselectivity. A plausible catalytic cycle was proposed for this asymmetric hydrogenation according to the results of deuterium-labeling experiments.
Article
Chemistry, Multidisciplinary
Fanfu Guan, Yu Qian, Peiqi Zhang, Runtong Zhang, Xumu Zhang, Jialin Wen
Summary: A novel microreactor (Flashstop reactor) combining flash chemistry and radial synthesis was designed to study the isomerization process of hydroformylation by a Rh/tetraphosphite catalyst in seconds. The initial 313 seconds showed the isomerization of 60-99% of 1-octene to 2- and 3-octenes before aldehyde formation, with two different types of isomerization reactions being observed. A monohydride complex without CO ligand was proposed to account for the ultrafast isomerization in the first 30 seconds, and the isomerization rate with this complex was calculated to be faster than the well-known H(CO)Rh(P-P) species. Experimental and DFT computational studies support this assumption, showing that the Flashstop reactor is a powerful tool for analyzing kinetics in gas-liquid biphasic reactions in seconds to minutes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jianrong Steve Zhou, Luoqiang Zhang, Xiuhua Wang, Maoping Pu, Caiyou Chen, Peng Yang, Yun-Dong Wu, Yonggui Robin Chi
Summary: Nickel catalysts with chiral pyrox ligands were used for enantioselective reductive arylation and heteroarylation of aldimines using (hetero)aryl halides and sulfonates. Crude aldimines generated from the condensation of aldehydes and azaaryl amines can also be used for catalytic arylation. The mechanism involves an elementary step of 1,4-addition of aryl nickel(I) complexes to N-azaaryl aldimines, as supported by density functional theory (DFT) calculations and experiments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Caiyou Chen, Gregory C. C. Fu
Summary: Carbon-oxygen bonds are common in organic molecules, making methods for their construction with control of stereoselectivity important. The widely used Williamson ether synthesis has limitations in terms of scope and stereochemistry due to its reaction mechanism. Transition-metal catalysis has the potential to overcome these limitations but progress has been limited, especially in controlling enantioselectivity. We demonstrate that a readily available copper catalyst can achieve enantioconvergent substitution reactions of α-haloamides with oxygen nucleophiles, offering a promising solution to the challenge of enantioselective alkylations of heteroatom nucleophiles.
Article
Chemistry, Organic
Chenzong Li, Xun Xiang, Xianghe Zhang, Zhao-Lin He, Shuang-Xi Gu, Xiu-Qin Dong
Summary: Chiral benzoxazinones and 4H-3,1-benzoxazines are important motifs found in pharmaceuticals and biological molecules. This study successfully developed a kinetic resolution process for racemic benzoxazinones through iridium-catalyzed asymmetric intramolecular allylation, providing a wide range of chiral benzoxazinones and 4H-3,1-benzoxazines with excellent results. The protocol demonstrated broad substrate scope and good functional group tolerance, and the chiral 4H-3,1-benzoxazine products could be easily transformed into other useful optically active heterocycles.
Article
Multidisciplinary Sciences
Qingyang Zhao, Le Yu, Yao-Du Zhang, Yong-Qiang Guo, Ming Chen, Zhi-Hui Ren, Zheng-Hui Guan
Summary: In this study, a selective C(alkyl)-C(vinyl) bond cleavage strategy was achieved through a transient directing group mediated retro-Diels-Alder reaction. This unprecedented strategy exhibits good tolerances and offers new opportunities for late-stage modifications of complex molecules.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Lei Yang, Xuefeng Tan, Menglong Zhao, Jialin Wen, Xumu Zhang
Summary: A ferrocene-based tetradentate ligand with modular synthesis and rigid skeleton was designed and synthesized, and its iron(II) complex was found to facilitate the asymmetric direct hydrogenation of ketones without the need for strong-field ligands such as CO and isocyanide. The use of a hydride donor LiAlH4 converted non-reactive Fe(II) species to reactive Fe(II) hydride species, enabling the preparation of various chiral alcohols with satisfactory yields and enantioinduction, including the intermediate for montelukast.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Liyao Zeng, Menglong Zhao, Bijin Lin, Jingyuan Song, James H. R. Tucker, Jialin Wen, Xumu Zhang
Summary: A new cobalt catalytic system for asymmetric hydrogenation of ketones was developed using ferrocene-based secondary phosphine oxide ligands. The coordination pattern of cobalt with the ligands was confirmed by X-ray diffraction. The cobalt complexes exhibited high reactivities (up to 99% yield) and good to excellent enantioselectivities (up to 92% ee) in the hydrogenation of ortho-substituted diaryl ketones. Moreover, the diferrocenyl cobalt complex showed intriguing UV-vis absorption and electrochemical properties.
Article
Chemistry, Organic
Shiyu Xiang, Taotao Lu, Junjun Liu, Qingyang Zhao
Summary: An unprecedented redox transformation of β-sulfinyl esters to generate sulfinate anions has been discovered, enabling the asymmetric sulfonylation of vinylidene o-quinone methides and providing various sulfone-based axially chiral styrenes with excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Bing-Ke Zhu, Hui Xu, Lu Xiao, Xin Chang, Liang Wei, Huailong Teng, Yanfeng Dang, Xiu-Qin Dong, Chun-Jiang Wang
Summary: Highly diastereo-/enantioselective assembly of 2,3-fused indolizine derivatives could be achieved through a cascade allylation/Friedel-Crafts type reaction enabled by a synergistic Cu/Ir catalysis. This method provides a facile route to enantioenriched indolizines with three stereogenic centers, showing excellent stereoselective control and broad substrate generality. The synthetic utility of this method was demonstrated by gram-scale reactions and transformations to other important chiral indolizine derivatives.
Article
Chemistry, Multidisciplinary
Jixing Li, Ming Fang, Maoyan Liao, Hongling Xie, Xiu-Qin Dong, Zhengyu Han, Jianwei Sun, Hai Huang
Summary: A tandem strategy has been developed for the synthesis of medium-sized heterocycles from oxetanes through the allylic amination/ring-opening of oxetanes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Cong-Shuai Wang, Qi Xiong, Hui Xu, Hao-Ran Yang, Yanfeng Dang, Xiu-Qin Dong, Chun-Jiang Wang
Summary: A novel organocatalytic method for the synthesis of axially chiral N,N'-pyrrolylindoles based on o-alkynylanilines has been successfully developed using chiral phosphoric acid as the catalyst. This strategy allows for the efficient and selective synthesis of N,N'-pyrrolylindoles with excellent yields and enantioselectivity. Preliminary biological activity studies show that these compounds exhibit promising cytotoxicity against various cancer cell lines.
Article
Chemistry, Multidisciplinary
Runtong Zhang, Xin Yan, Shao-Tao Bai, Caiyou Chen, Bozhao Nan, Baode Ma, Jialin Wen, Xumu Zhang
Summary: This paper reports a dual metal catalysis system combining a Ru-isomerization catalyst and a Rh-linear-hydroformylation catalyst for the production of value-added linear aldehydes from C4 raffinate and internal olefins. The optimized dual metal catalyst system showed high selectivity and conversion for the synthesis of linear aldehydes.
GREEN SYNTHESIS AND CATALYSIS
(2022)