Article
Chemistry, Organic
Xiaoxiao Xie, Sanliang Li, Qiaoyu Chen, Hao Guo, Junfeng Yang, Junliang Zhang
Summary: This article presents a novel method for the synthesis of chiral phosphorus ligands, and demonstrates their potential applications in catalytic asymmetric reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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, Multidisciplinary
Yong Yuan, Xue Liu, Jingcheng Hu, Pengjie Wang, Shengchun Wang, Hesham Alhumade, Aiwen Lei
Summary: In this study, a facile and novel electrochemical method was developed for the synthesis of tertiary phosphines with excellent yields. The protocol showed good reaction selectivity and scalability.
Article
Chemistry, Organic
Pep Rojo, Antoni Riera, Xavier Verdaguer
Summary: The efficient electrophilic P-stereogenic transfer reagent BOM-tert-butylmethylphosphinite borane was used for the synthesis of bulky tertiary phosphines with high stereospecificity in a one-pot deprotection/substitution reaction. A wide range of tertiary phosphines in excellent enantiomeric excess was synthesized using this method, including a bulky P-stereogenic BisP* ligand analogue.
Article
Chemistry, Physical
Archana Rajmane, Arjun Kumbhar
Summary: In recent years, Pd-catalyzed cross-coupling reactions have been widely used in various fields of chemistry. However, traditional phosphine ligands used in these reactions have limitations. Therefore, phosphine-free ligands and mixed donor P, N-ligands have attracted attention for their advantages in catalysis.
MOLECULAR CATALYSIS
(2022)
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
Multidisciplinary Sciences
Liangzhi Pang, Zhan Huang, Qilin Sun, Gen Li, Jiaojiao Liu, Baoli Li, Congyue Ma, Jiaxu Guo, Chuanzhi Yao, Jie Yu, Qiankun Li
Summary: Chiral monodentate biaryl phosphines (MOPs) have been extensively studied as chiral ligands. The authors demonstrate a diverse synthesis method for structurally diverse MOPs containing both phosphorus and axial chirality. They employ a distinct strategy for diversity-oriented synthesis, enabled by the enantioselective cleavage of C-P bond, to create chiral Pd-II intermediates that can be transformed into enantioenriched MOPs with high diastereo- and enantioselectivities. These chiral MOPs show excellent catalytic properties in the asymmetric [3 + 2] annulation reaction, leading to the formation of chiral functionalized bicyclic imide.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Bing Chen, Damian Padin, Charlotte. N. N. Stindt, Ben. L. L. Feringa
Summary: In this paper, a novel strategy for the stereocontrolled synthesis of versatile chiral P-stereogenic alkenylphosphonamidates is reported. This strategy involves a one-pot Ni-catalyzed C-P coupling/diastereoselective hydrolysis of readily available phosphoramidites and alkenyl halides. The reaction conditions were found to exhibit chemo- and diastereodivergent behavior, and the chiral alkenylphosphonamidates obtained can be selectively derivatized for the synthesis of structurally diverse P-stereogenic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bin Zhang, Wen-Qing Zhou, Xu-Teng Liu, Yingying Sun, Qing-Wei Zhang
Summary: We report an efficient method for the synthesis of P-stereogenic alkynylphosphines with high enantioselectivity via a Ni-catalyzed asymmetric cross-coupling reaction, providing a new approach to the derivatization of phosphine compounds.
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, Multidisciplinary
Saima Perveen, Shuai Zhang, Linghua Wang, Peidong Song, Yizhao Ouyang, Jiao Jiao, Xin-Hua Duan, Pengfei Li
Summary: The first nickel-catalyzed highly enantioselective reductive Ullmann coupling of ortho-chlorinated aryl aldehyde was achieved under mild reaction conditions using a chiral 2,2'-bipyridine ligand (+)-DTB-SBpy, resulting in the synthesis of axially chiral biphenyl or binaphthyl dials with high yields and enantioselectivities. The versatility of the products as common synthetic intermediates for diverse axially chiral ligands, catalysts, and functional molecules was demonstrated through short-step transformations. Additionally, this protocol enabled the concise and highly enantioselective formal total synthesis of biologically active natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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, Multidisciplinary
Jie Kang, Kang Ding, Si-Mu Ren, Bo Su
Summary: We report a highly enantioselective dynamic kinetic intermolecular P-C coupling of secondary phosphine oxides (SPOs) and aryl iodides catalyzed by copper complexes ligated by a finely modified chiral 1,2-diamine ligand. The reaction tolerates a wide range of substrates, providing P-stereogenic phosphine oxides in high yields and with good enantioselectivity. The resulting enantioenriched products can be transformed into structurally diverse P-chiral scaffolds, which are valuable in asymmetric synthesis as ligands and catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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, Organic
Xiao Yi, Yirui Chen, An Huang, Dingguo Song, Jiaying He, Fei Ling, Weihui Zhong
Summary: A series of novel chiral ligands were developed for the synthesis of beta-amino alcohols with high enantioselectivity and broad substrate scope, enabling late-stage functionalization of drugs and natural products. Density-functional-theory studies were in good agreement with experimental results.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Zhenya Li, Ronghua Xu, Huichuang Guo, He Yang, Guangqing Xu, Enxue Shi, Junhua Xiao, Wenjun Tang
Summary: Highly enantioselective hydrogenation of (Z)-N-sulfonyl-α-dehydroamido boronic esters using a JosiPhos-type ligand is realized for the first time. This method enables the convenient synthesis of a series of enantio-enriched N-sulfonyl-α-amido boronic esters with good yields and excellent enantioselectivities (up to 99% ee).
Article
Chemistry, Multidisciplinary
Bowen Li, Bangke Luo, He Yang, Wenjun Tang
Summary: This study reports an efficient palladium-catalyzed Heck reaction for the synthesis of heterocycles with α-heteroaryl substitution. The method exhibits a broad substrate scope and excellent functional group compatibility. The use of a sterically bulky ligand containing an anthryl moiety is crucial for this transformation. Additionally, an asymmetric variant of the Heck reaction has been achieved, enabling the efficient asymmetric synthesis of (S)-nicotine and its analogues via a cationic palladium pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Peixin Wang, Qinglong Zhang, Wenjun Tang, Weiwei Zi
Summary: The aldol reaction is an important and versatile transformation in organic synthesis, but achieving stereoselectivity for the formation of diastereomeric products is challenging. In this study, a new catalytic system was developed to overcome the selectivity limitations of the reaction. Computational studies provided insights into the reaction mechanism and stereochemistry of the catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jinbin Zhu, Zhenyue Li, Jiaqi Li, Duanshuai Tian, Ronghua Xu, Zhiyong Tan, Zhengwang Chen, Wenjun Tang
Summary: In this report, an efficient rhodium-catalyzed addition of arylboronic acids to N-heteroaryl ketones is established, affording a variety of valuable alpha-heteroaryl alcohols with excellent functional group compatibility. The employment of the WingPhos ligand containing two anthryl groups is crucial for this transformation.
Article
Chemistry, Organic
Ben Gao, Yuqi Chang, Wenjun Tang
Summary: In this study, a machine learning black-box model was built to predict the enantiomeric excess value of asymmetric transfer hydrogenation reactions. Molecular descriptors were extracted as features based on DFT calculations, which were then inputted into the machine learning model to calculate the enantiomeric excess value. The results showed that our model performed the best on this dataset, with a test-set root-mean-square error of 8.6 and a coefficient of determination R-2 of 0.86 compared to the experimental value. The model can be used for predicting the enantiomeric excess value for asymmetric transfer hydrogenation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Mingkang Zhou, Yaodong Lin, Xiao-Xuan Chen, Guangqing Xu, Lung Wa Chung, Wenjun Tang
Summary: We report the chiral diboron-templated asymmetric homocoupling of aryl alkyl ketimines, leading to the formation of chiral vicinal tetrasubstituted diamines with high enantioselectivities and good to high yields. This powerful and efficient reaction is achieved by rational design and engineering of chiral diborons, which participate in a [3,3]-sigmatropic rearrangement. DFT studies reveal that different conformational assembling strategies of chiral diborons ensure the excellent enantioselectivity in the tight concerted transition states.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiawei Sun, Yuan Chen, Sherif Shaban Ragab, Wei Gu, Ziqiang Tang, Yuexun Tang, Wenjun Tang
Summary: In this study, an unsaturation-functionalization strategy was applied to address the C19-hydroxylation issue for efficient synthesis of polyhydroxylated steroids. The synthetic method featured an effective asymmetric dearomative cyclization and various reactions to introduce the polyhydroxy functionalities. Ultimately, the total synthesis of 19-hydroxysarmentogenin and ouabagenin was achieved, demonstrating the synthetic versatility and practicality of these polyhydroxylated steroids in the search for new therapeutic agents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xinlong Yan, Zongwei Li, Lin Fan, Jiashan Li, Guodu Liu
Summary: In recent years, new methods for the preparation of chiral alkyl fluorides have been intensively studied due to their favorable physicochemical and biological properties. In this study, the regio- and enantio-selective allylic alkylation of alpha-pyridyl-alpha-fluoroesters with allyl acetates, promoted by Cu/Pd synergistic catalysis, was described, leading to the construction of carbon-fluorine quaternary stereocenters. The palladium catalyst primarily formed the C-C bond, while the chiral copper catalyst controlled the enantioselectivity. The reaction showed high yield, excellent enantioselectivity, and E/Z selectivity (up to 98% yield, 98:2 er, E/Z>20:1) with a series of aryl- and aliphatic-substituted allyl acetates.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Review
Chemistry, Organic
Changjiang Li, Zhaozhou Li, Kunpeng Tan, Guodu Liu
Summary: Rhodium-catalyzed hydroformylation of olefins is a significant method for synthesizing aldehydes, and the regioselectivity and enantioselectivity of the product controlled by ligands are commonly used strategies. The modular synthesis of phosphite and phosphoramidite ligands has advantages of simple synthesis and high catalytic activity, thus being widely used in hydroformylation reactions. This review focuses on the synthesis methods and design ideas of such ligands, as well as their application effects in hydroformylation reactions, aiming to provide a reference for ligand design and synthesis in subsequent hydroformylation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wen-Jun Tang, Shu-Min Dai, Yue Yuan, Shuai Wang, Yu-Peng He, Fang Yu
Summary: The direct methoxylation of substituted phenylalanines has been achieved through methoxyiminoacyl (MIA)-mediated Pd-catalyzed C-H functionalization, resulting in the efficient synthesis of diverse ortho-methoxylated phenylalanine derivatives in good to high yields. Kinetic isotope effect studies reveal that the oxhydryl cleavage step is the rate-limiting step. Computational data demonstrate that the manner in which methanol participates greatly influences the energy barriers of transition states during the C(sp2)-O formation stage, with stepwise deprotonation and reductive elimination being superior to concerted deprotonation-methoxylation.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Applied
Yuxue Cao, Guodu Liu
Summary: Chiral phosphoric acid has been a crucial catalyst in chemical synthesis for over five decades. However, a revolutionary approach using photocatalytic excitation of molecules to generate free radicals has emerged in recent years, surpassing the limitations of traditional organic synthesis methods. A significant area of research focuses on chiral phosphoric acid synergistic photocatalysis for enantioselective chemical synthesis, utilizing a bifunctional hydrogen-bonding catalyst.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Lin Fan, Xinlong Yan, Changjiang Li, Yuxue Cao, Guodu Liu
Summary: In this study, a Cu-catalyzed intramolecular borylation-cross coupling reaction was developed, enabling the synthesis of both racemic and chiral borylated indolines. The reaction involved the simultaneous construction of C-C and C-B bonds using a Cu/phosphine ligand system. The method exhibited good to excellent yields and short reaction times. Asymmetric synthesis was also investigated, resulting in the successful synthesis of a chiral borylated indoline compound.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
He Yang, Hanxiao Yu, Izabela A. Stolarzewicz, Wenjun Tang
Summary: In the past two decades, there has been a significant increase in the proportion of approved chiral drugs and drug candidates under medical studies. This has posed a challenge for medicinal and process chemists in efficiently synthesizing enantiopure pharmaceuticals. However, the development of asymmetric catalysis has provided an effective solution to this challenge, promoting drug discovery and industrial production of active pharmaceutical ingredients in an economic and environmentally friendly manner. This review summarizes the recent applications of asymmetric catalysis in the pharmaceutical industry, showcasing the achievements and trends in the asymmetric synthesis of therapeutic agents using state-of-the-art technologies.
Article
Chemistry, Organic
Ziyue Liu, Ben Gao, Konstantin Chernichenko, He Yang, Sebastien Lemaire, Wenjun Tang
Summary: An enantioselective palladium-catalyzed C-H arylation of functionalized pyrazoles/triazoles/imidazoles has been developed, yielding axially chiral ortho-nitro/formyl-substituted heterobiaryls with high enantioselectivity and good yields.
Review
Chemistry, Organic
Xinlong Yan, Lin Fan, Xiangdong Zhang, Guodu Liu
Summary: Transition metal-catalyzed carbonylation is a powerful and versatile strategy to synthesize complex carbonyl-containing molecules from simple feedstocks. Copper-catalyzed carbonylation using CO as the C(1) source has shown advantages of low cost and toxicity compared to noble metal catalysts. Recent advances in this field have summarized the conversion of easily accessible substrates into valuable carbonylated products, providing a greener alternative for catalytic carbonylation.
ORGANIC CHEMISTRY FRONTIERS
(2022)
