Article
Chemistry, Multidisciplinary
Peng Lu, Hongliang Wang, Yihui Mao, Xin Hong, Zhan Lu
Summary: Investigation on asymmetric hydrogenation of olefins is vital for the synthesis of pharmaceutical molecules and chemical industry. A cobalt-catalyzed enantioconvergent hydrogenation method has been developed for common minimally functionalized E/Z-olefin mixtures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Congcong Yin, Yingmin Pan, Longsheng Zheng, Bijin Lin, Jialin Wen, Xumu Zhang
Summary: Enantioselective hydrogenation of imines via an outer-sphere mechanism was achieved using an iridium tridentate catalyst, resulting in high enantioselectivities and turnover numbers up to 10,000. This method was successfully applied in the synthesis of chiral amines with an alpha-stereocenter, allowing for the preparation of cinacalcet with remarkably high enantioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Sairam Mudulkar, Sai Teja Kolla, Balasubramanian Sridhar, China Raju Bhimapaka
Summary: A new BF3 center dot OEt2-catalyzed approach has been developed for the synthesis of 2,2'-spirobi-2H-1-benzopyrancarboxylates. The reaction involves the formation of C-C and C-O bonds simultaneously in one pot. Structure confirmation of compound 3c was achieved by single crystal X-ray analysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Organic
Suna Han, Xin Shen, Xiaoxue Wu, Chaochao Xie, Guofu Zi, Guohua Hou
Summary: In this study, a Cu-catalyzed highly diastereo- and enantioselective methylboration reaction of diverse heterocyclic compounds was realized for the first time. The reaction provides the corresponding organoboron compounds bearing two adjacent chiral centers with excellent diastereoselectivities and enantioselectivities. This method offers an efficient and highly enantioselective approach for the synthesis of chiral organoboron compounds and their derivatives containing heterocyclic structures.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Haibo Wu, Hao Su, Erik J. Schulze, Bram B. C. Peters, Mark D. Nolan, Jianping Yang, Thishana Singh, Marten S. G. Ahlquist, Pher G. Andersson
Summary: The study presents a highly efficient desymmetrization of 1,4-dienes through iridium-catalyzed site- and enantioselective hydrogenation, allowing the installation of two adjacent stereogenic centers. High yields and excellent selectivities were achieved for a range of substrates, and the methodology was demonstrated by synthesizing key intermediates of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Guiying Xiao, Chaochao Xie, Qianling Guo, Guofu Zi, Guohua Hou, Yuping Huang
Summary: A highly efficient asymmetric hydrogenation method has been developed for the synthesis of chiral gamma-hydroxy acid derivatives. The method shows excellent enantioselectivity and has the potential to be applied in the synthesis of chiral compounds and key intermediates for pharmaceutical synthesis.
Article
Chemistry, Organic
Song Feng, Baoqi Ren, Lige Li, Fengmin Xia, Zhiyong Tang, Yu Zhang, Xiaoning Liu, Qixuan Lu, Wenge Zhong
Summary: This method achieves the N-heteroaryl-directed Ru-catalyzed asymmetric hydrogenation of α,α-disubstituted vinyl ethers with good to excellent enantioselectivities, providing an attractive approach for synthesizing pharmaceutically active heteroaryl compounds containing chiral ether units.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Huimin Qi, Lixian Wang, Qiangsheng Sun, Wei Sun
Summary: This article describes a stable iridium catalyst with a chiral 2-pyridyl imidazoline ligand for the asymmetric transfer hydrogenation (ATH) of quinolines and N-heteroaryl compounds. The ATH system uses formic acid as the hydrogen source and water as the solvent. Various quinolines and N-heteroaryl compounds can be efficiently converted into desired products with moderate to good enantioselectivity at a catalyst loading as low as 0.001 mol% under mild conditions.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Physical
Catherine Gazolla Santana, Michael J. Krische
Summary: Catalytic carbonyl reductive couplings facilitated by hydrogenation, transfer hydrogenation, and hydrogen autotransfer allow unsaturated hydrocarbons to substitute organometallic reagents for C-C bond formation without the need for stoichiometric metals, addressing issues of safety and challenges in large-scale implementation.
Article
Chemistry, Multidisciplinary
Peng Lu, Xiang Ren, Haofeng Xu, Dongpo Lu, Yufeng Sun, Zhan Lu
Summary: This study presents an iron-catalyzed highly enantioselective hydrogenation method for the synthesis of chiral alkanes from minimally functionalized 1,1-disubstituted alkenes. A novel chiral 8-oxazoline iminoquinoline ligand and its iron complex have been designed and synthesized to facilitate this transformation. The reaction is operationally simple, utilizing 1 atm of hydrogen gas, and demonstrates good functional group tolerance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Andres Arribas, Martin Calvelo, David F. Fernandez, Catarina A. B. Rodrigues, Jose L. Mascarenas, Fernando Lopez
Summary: The study presents a versatile and highly enantioselective intramolecular hydrocarbonation reaction for the synthesis of heteropolycyclic systems with chiral quaternary carbon stereocenters. The method relies on an iridium-(I)/bisphosphine chiral catalyst, yielding fused indole and pyrrole products with high enantiomeric excesses. DFT computational studies provided a detailed mechanistic profile and identified weak non-covalent interactions as key factors controlling the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Cong Fu, Xin Chang, Lu Xiao, Chun -Jiang Wang
Summary: In this study, a one-pot Cu-mediated H-D exchange using inexpensive heavy water as the deuterium source, followed by Cu- and Ir-catalyzed stereodivergent allylic alkylation, has been developed to efficiently access enantioenriched alpha-deuterium-labeled alpha-amino acids.
Article
Chemistry, Multidisciplinary
Pep Rojo, Medea Molinari, Albert Cabre, Clara Garcia-Mateos, Antoni Riera, Xavier Verdaguer
Summary: Chiral compounds containing nitrogen heteroatoms are crucial for the chemical, pharmaceutical, and agrochemical industries. In this study, a series of P-stereogenic phosphinooxazoline iridium catalysts were synthesized and successfully used in the asymmetric hydrogenation of N-Boc-2,3-diarylallyl amines, achieving high enantioselectivity. The synthetic utility of the obtained 2,3-diarylpropyl amines was also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Rurong Yu, Feiyue Hao, Xinyu Zhang, Zhongbing Fang, Zhengneng Jin, Guyue Liu, Guoliang Dai, Jiashou Wu
Summary: A method for selectively reducing 2-pyridyl ketones and related N-heteroaryl compounds using cobalt stearate as a catalyst and DMF as a hydride source has been developed. The chelation with cobalt activates the ketone substrate, making this method highly chemoselective. A possible reaction mechanism has been proposed based on control experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guanlin Li, Ling Zhao, Yicong Luo, Youbin Peng, Kai Xu, Xiaohong Huo, Wanbin Zhang
Summary: Asymmetric desymmetrization is a powerful strategy for building stereocenters in asymmetric synthesis. This study reports a Pd/Cu catalyzed asymmetric desymmetrization reaction using a simple geminal dicarboxylate, which achieved good yields and high selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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.
Article
Chemistry, Multidisciplinary
Jingjing Li, Jianxun Ye, Jiayu Zhou, Jing Li, Delong Liu, Wanbin Zhang
Summary: The efficient RuPHOX-Ru catalyzed asymmetric hydrogenation of alpha-substituted tetralones via a dynamic kinetic resolution has been achieved for the synthesis of chiral tetrahydronaphthols. The mechanism study revealed that hydrogenation with H-2 gas is predominant in the reaction pathway compared to transfer hydrogenation with EtOH solvent as the hydrogen source.
CHEMICAL COMMUNICATIONS
(2022)
