Article
Multidisciplinary Sciences
Jie Wang, Wei-Feng Zheng, Xue Zhang, Hui Qian, Shengming Ma
Summary: This study reports the synthesis of non-readily available enantioenriched tetrasubstituted allenes through rhodium-catalyzed reactions controlled by steric hindrance. Detailed mechanistic experiments and density functional theory studies reveal the mechanism behind the formation of different stereochemistry under different reaction conditions. A stereodivergent protocol to construct the enantiomer of optically active tetrasubstituted allenes from the same starting materials is successfully developed based on these mechanistic understandings.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yirui Chen, Xiao Yi, Yuqi Cheng, An Huang, Zehui Yang, Xianghua Zhao, Fei Ling, Weihui Zhong
Summary: A highly efficient Rh-catalyzed hydrogenation method has been developed using a new family of highly rigid chiral ferrocenylphosphine-spirophosphonamidite ligands, with excellent enantioselectivity achieved. This catalytic system can be applied in the scalable synthesis of highly optically pure key intermediates for drug production.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Gang Liu, Congcong Yin, Xuanliang Yang, Anqi Li, Minyan Wang, Xumu Zhang, Xiu-Qin Dong
Summary: A highly chemo- and enantioselective hydrogenation method for beta-sulfonyl-alpha,beta-unsaturated ketones was successfully developed, producing a variety of enantioenriched gamma-ketosulfones in good to high yields with excellent selectivities. Gram-scale asymmetric hydrogenation was carried out smoothly with high yields and selectivities. Preliminary DFT computations provided a reasonable explanation for the observed high chemoselectivity and enantioselectivity.
Article
Chemistry, Organic
Kun Guo, Qian Zeng, Alba Villar-Yanez, Carles Bo, Arjan W. Kleij
Summary: A Ni-catalyzed decarboxylative silylation of alkynyl cyclic carbonates has been reported, which serves as versatile propargylic surrogates and affords a wide range of highly substituted 2,3- and 3,4-allenol products in good yields. The formal cross-coupling between a tentative intermediate Ni(allenyl) and the silyl reagent can be further extended to enantiospecific conversions providing access to chiral allene synthons. This study is of significance as it represents the first Ni-catalyzed propargylic silylation proceeding through an S(N)2' manifold.
Article
Chemistry, Organic
Chao Dong, Dao-Sheng Liu, Lei Zhang, Xiang-Ping Hu
Summary: An enantioselective Rh-catalyzed hydrogenation of E/Z mixtures of trisubstituted vinyl esters has been achieved using a chiral ferrocenylphosphine-phosphoramidite ligand. The reaction showed high yields and good to high enantioselectivities, with the presence of a small amount of t-butanol benefiting the hydrogenation outcome.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Victor Garcia-Vazquez, Pablo Martinez-Pardo, Alexandru Postole, A. Ken Inge, Belen Martin-Matute
Summary: This study developed a method for synthesizing chiral trifluoromethylated aliphatic amines, which involves organocatalytic isomerization and imine/enamine reduction to obtain compounds with two noncontiguous stereogenic centers in high yields and selectivities. The method is effective for primary amine substrates and provides a new pathway for synthesizing chiral trifluoromethylated scaffolds.
Article
Chemistry, Organic
Chaoqiong Wang, Fang Xie, Qianling Guo, Chaochao Xie, Guofu Zi, Weiping Ye, Zhangtao Zhou, Guohua Hou, Zhanbin Zhang
Summary: The first asymmetric hydrogenation of beta,beta-diaryl unsaturated phosphonates has been achieved with excellent enantioselectivities using the Rh-(R, R)-f-spiroPhos complex as catalyst. This method also shows comparable performance for beta-aryl-beta-alkyl unsaturated phosphonates, providing chiral phosphonates with high ee values. This new methodology offers a straightforward approach to asymmetric synthesis of chiral phosphonates.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xin Liu, Thomas Werner
Summary: A manganese pincer complex is reported as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes, leading to the corresponding alcohols, amines, and methanol. This method represents an approach to the indirect reduction of CO2 and shows the first examples of reduction of carbamates and urea derivatives as well as C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is demonstrated by successful reduction of various compounds with good to excellent yields.
Article
Chemistry, Multidisciplinary
Xintuo Yang, Xiang Li, Pinhong Chen, Guosheng Liu
Summary: A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. The (EtO)(2)MeSiH/BQ redox system is crucial for the highly selective and efficient hydrooxygenation, where alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced by silane. This method provides an efficient access to optically pure alcohol esters from easily available alkenes with excellent enantioselectivities and features a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Ju-Song Yang, Ka Lu, Chen-Xiao Li, Zu-Hang Zhao, Fu-Min Zhang, Xiao-Ming Zhang, Yong-Qiang Tu
Summary: A nickel hydride-catalyzed regio- and enantioselective hydroalkylation reaction was developed to access a library of chiral beta- or gamma-branched aromatic N-heterocycles. This intriguing asymmetric transformation features excellent selectivities, step- and atom-economies, and generates two kinds of chiral products through one synthetic strategy. The possible reaction mechanism was extensively investigated using numerous control experiments and density functional theory calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yaowen Liu, Martin C. Dietl, Chunyu Han, Matthias Rudolph, Frank Rominger, Petra Kraemer, A. Stephen K. Hashmi
Summary: Multisubstituted alkenes can be efficiently synthesized by a gold-catalyzed acyloxyalkynylation reaction, which proceeds under mild conditions and accepts a wide range of substrates, resulting in high yields.
Article
Chemistry, Organic
Yanfang Han, Long Zhang, Sanzhong Luo
Summary: A highly diastereo- and enantioselective retro-Claisen reaction has been developed using chiral primary amine catalysis. This reaction enables efficient synthesis of chiral beta,beta-diaryl-alpha-branched ketones with excellent stereoselectivities. The reaction proceeds through a tandem sequence involving benzylic C-C bond formation, C-C bond cleavage, and stereospecific enamine protonation. The use of o-quinone methides as diaryl precursors allows for a broad substrate scope, mild reaction conditions, and a high degree of stereocontrol.
Article
Chemistry, Multidisciplinary
Wenke Dong, Xin Xu, Honghui Ma, Yaqin Lei, Zhenyang Lin, Wanxiang Zhao
Summary: Researchers reported a catalytic enantioselective hydroboration of silyl enol ethers (SEEs) using two new chiral phosphine ligands, featuring mild reaction conditions and a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Ju-Song Yang, Ka Lu, Chen-Xiao Li, Zu-Hang Zhao, Fu-Min Zhang, Xiao-Ming Zhang, Yong-Qiang Tu
Summary: A nickel hydride-catalyzed hydroalkylation reaction was developed for the synthesis of a library of chiral aromatic N-heterocycles. The reaction demonstrated excellent selectivities, step- and atom-economies, and resulted in two kinds of chiral products through one synthetic strategy. The possible reaction mechanism was extensively investigated using control experiments and density functional theory calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Nan Ji, Qinqin Tian, Qingqing Yang, Minghua Li, Wei He
Summary: This study describes a highly enantioselective epoxidation of trans-alpha-cyano-alpha, beta-unsaturated esters using cinchona alkaloid-derived urea and H2O2 as organocatalysts and oxidant, resulting in chiral glycidic ester derivatives with cyano groups in good yields (up to 95%) and excellent enantioselectivities (up to 97% ee). A plausible transition state was proposed for the reaction mechanism.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Jing Li, Feng Gao, Tanveer Ahmad, Yicong Luo, Zhenfeng Zhang, Qianjia Yuan, Wanbin Zhang
Summary: TBAJ-876, a new anti-tuberculosis drug developed by TB Alliance, has entered Phase II clinical trials. In this study, the first asymmetric synthesis of TBAJ-876 was achieved using synergistic Li/Li catalysis with a high yield of 95% and a stereoselectivity of 88:12 (99.6:0.4, 10:1 dr after simple recrystallization). Furthermore, the mechanism of the synergistic reaction was elucidated through DFT calculations and Li-7-NMR analysis, showing the activation of nucleophile and electrophile by chiral and achiral Li-complexes, respectively. Additionally, the scalability of this protocol was demonstrated at a 5-gram scale, indicating its potential for industrial application.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Chandi C. Malakar, Luca Dell'Amico, Wanbin Zhang
Summary: Dual catalysis is a powerful strategy for chemical reactions in organic synthesis, with advantages such as increased reactivity, control of stereoselectivity, and stereodivergent synthesis. This Perspective aims to introduce the reader to the special collection on Dual Catalysis in EurJOC, summarizing the different categories of dual catalysis and demonstrating their benefits in constructing new chemical bonds selectively. It also presents current challenges and new trends in dual catalysis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Jiayu Zhou, Jianxun Ye, Yang Zhang, Zhaodi Li, Jingjing Li, Delong Liu, Wanbin Zhang
Summary: The RuPHOX-Ru catalyzed asymmetric hydrogenation of diaryl ketones has been developed, yielding chiral diaryl methanols with up to 99% yield and 99% ee. This protocol can be performed on a gram-scale with low catalyst loading (2000 S/C) and the resulting products are valuable for various transformations, especially in the synthesis of chiral drugs like (S)-Orphenadrine and (S)-Neobenodine. Deuterium labeling and control experiments revealed that the RuPHOX-Ru-catalyzed asymmetric hydrogenation is exclusively driven by H-2 as the hydrogen source.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Tiantian Chen, Yashi Zou, Yanhua Hu, Zhenfeng Zhang, Hao Wei, Liangming Wei, Wanbin Zhang
Summary: An efficient asymmetric hydrogenation of internal simple enamides has been achieved using the diphosphine-cobalt-zinc catalytic system. The Ph-BPE ligand can achieve convergent asymmetric hydrogenation of E/Z-substrates. High yields and excellent enantioselectivities were obtained for different types of enamides. The hydrogenated products can be used for the synthesis of useful chiral drugs. Reasonable catalytic mechanism and stereocontrol mode are proposed based on DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yu Nie, Qianjia Yuan, Wanbin Zhang
Summary: The design and synthesis of chiral ligands play a vital role in asymmetric catalytic reactions. Our group has developed a novel chiral PHOX ligand with an axis-unfixed biphenyl backbone, which exhibits interesting coordination behavior and excellent chiral inducing ability in various transition-metal-catalyzed asymmetric reactions. This personal account provides an overview of the design and applications of our developed BiphPHOX ligand, aiming to inspire the exploration of novel ligands and related reactions.
Article
Chemistry, Organic
Tanveer Ahmad, Feng Gao, Jing Li, Zhenfeng Zhang, Tao Song, Qianjia Yuan, Wanbin Zhang
Summary: TBAJ-587, an analogue of bedaquiline (BDQ), exhibits high bacterial potency, low toxicity, and improved pharmacokinetic profile compared to the parent molecule. The first asymmetric synthesis of TBAJ-587 using a synergistic Li/Li bimetallic system is reported, achieving a yield of 90% and an enantiomeric ratio of 80:20. This efficient synthesis method can be scaled up for clinical drug production.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhengxing Wu, Jingjie Meng, Huikang Liu, Yunyi Li, Xiao Zhang, Wanbin Zhang
Summary: In this study, a palladium-catalyzed aerobic oxidative method was developed for the multi-site programmable functionalization of terminal olefins. The reaction sequence between alkene isomerization and oxidative functionalization was controlled, and a variety of functionalized products were obtained, including unsaturated alcohols, polyalcohols, monosaccharides, and C-glycosides.
Article
Chemistry, Physical
Tao Song, Yicong Luo, Kuiyang Wang, Bingyi Wang, Qianjia Yuan, Wanbin Zhang
Summary: This research presents an efficient nickel-catalyzed remote hydroamination and hydroetherification method, which allows the installation of amino or alkoxyl groups at C(sp3)-H positions that are far from the double bond of alkenes. The yields are as high as 93% with exclusive regioselectivities.
Review
Chemistry, Organic
Jingjie Meng, Huikang Liu, Zhengxing Wu, Wanbin Zhang
Summary: Amines are widely used in the chemical and pharmaceutical industries, and research on synthetic methods for their preparation is driven by their importance. The amination of alkenes is a direct and efficient method for the construction of amines, with oxidative amination being more valuable due to its ability to produce products with greater functionality and flexibility. The use of molecular oxygen as a terminal oxidant in oxidative amination shows promising application prospects. Recent advancements in palladium-catalyzed aerobic oxidative amination of alkenes are discussed, with a focus on the oxidation process and associated mechanisms.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Fei Li, Yicong Luo, Jinbao Ren, Qianjia Yuan, Deyue Yan, Wanbin Zhang
Summary: An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering functionalized products with good selectivities. The reaction showed excellent tolerance towards different functional groups and a wide substrate scope. Moreover, it successfully achieved the regioconvergent transformation of mixtures of isomeric alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yicong Luo, Yuqi Ma, Guanlin Li, Xiaohong Huo, Wanbin Zhang
Summary: In this study, a Pd/Cu/Li ternary system has been developed for the stereodivergent synthesis of chiral fluorinated amino acids. By sequential desymmetrization and allylic substitution reactions, non-natural amino acids with excellent selectivity can be synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tao Song, Kuiyang Wang, Qianjia Yuan, Wanbin Zhang
Summary: This study reports the nickel-catalyzed hydroamination and hydroalkoxylation reactions between unactivated amines and alcohols with enolactams. The method demonstrates good functional group tolerance and delivers the corresponding hydrofunctionalized products in good to excellent yields (& LE;98%). Additionally, an intramolecular hydroalkoxylation of an enolactam is successfully achieved, providing a cyclization product in good yield. Mechanistic studies reveal that tBuI plays crucial roles as a hydride donor and radical precursor for the reaction's success.
Editorial Material
Chemistry, Physical
Youbin Peng, Xiaohong Huo, Wanbin Zhang
Summary: In this article, Huang and co-workers describe a Pd-catalyzed stereodivergent [4 + 2] annulation reaction of alkylidene pyrazolones with vinyl benzoxazinanones via ligand regulation. The reaction produces an array of [6.5]-spiropyrazolones with three contiguous stereocenters in high yields and stereoselectivities. The origin of this stereodivergent annulation process was revealed by DFT calculation.
Article
Chemistry, Organic
Fei Li, Jinbao Ren, Yifan Song, Qianjia Yuan, Deyue Yan, Wanbin Zhang
Summary: In this study, an iridium-catalyzed 1,3-rearrangement of readily available allylic ethers was developed, providing access to allylic ethers with a large steric hindrance. The method exhibited a broad substrate scope and was applicable for the late-stage modification of several natural products. A possible reaction pathway was proposed based on control experiments.
