Article
Chemistry, Multidisciplinary
Huai-Yu Bin, Li Cheng, Xiong Wu, Chang-Liang Zhu, Xiao-Hui Yang, Jian-Hua Xie, Qi-Lin Zhou
Summary: An iridium-catalyzed asymmetric hydrogenation process was developed to convert racemic exocyclic gamma,delta-unsaturated beta-ketoesters into functionalized chiral allylic alcohols via dynamic kinetic resolution. The protocol exhibited high yields, good to excellent enantioselectivities (87 to >99% ee), and cis-selectivities (93 : 7 to >99 : 1), and was successfully applied in the enantioselective synthesis of chiral carbocyclic delta-amino esters and the beta-galactosidase inhibitor isogalactofagomine with a lower catalyst loading on gram scale.
Article
Chemistry, Organic
Hiroki Ishikawa, Taiga Yurino, Ryo Komatsu, Ming-Yuan Gao, Noriyoshi Arai, Taichiro Touge, Kazuhiko Matsumura, Takeshi Ohkuma
Summary: Racemic alpha-substituted alpha-amino esters were hydrogenated into enantioenriched beta-amino alcohols through dynamic kinetic resolution with chiral ruthenabicyclic complexes. The reaction proceeded with 1,2-hydride migration of the a-amino acetalate intermediate into the alpha-hydroxy imine followed by the continuous reduction of the imino compound, affording the amino alcohol product.
Article
Chemistry, Organic
Baixue Liu, Peng Liu, Xue Wang, Feng Feng, Zhen Wang, Wenqiang Yang
Summary: A general method for the gram-scale enantioselective synthesis of P-stereogenic cyclic phosphine oxides has been developed using copper-catalyzed dynamic kinetic resolution, leading to high yields and high enantioselectivities. The resulting products can be easily reduced to obtain useful P(III)-stereogenic cyclic phosphines. A proposed mechanism involves the unusual rapid racemization of SPOs.
Article
Chemistry, Applied
Fei Ling, Yifan Wang, An Huang, Ze Wang, Shiliang Wang, Jiayin He, Xianghua Zhao, Weihui Zhong
Summary: An iridium/f-diaphos catalytic system for the enantioselective hydrogenation of alpha-substituted beta-ketoesters via dynamic kinetic resolution was reported. The desired anti beta'-hydroxy-beta-amino esters were obtained in moderate to good yields with high enantioselectivity and diastereoselectivity. This protocol is tolerant to various functional groups and can be easily conducted on gram scale with lower catalyst loading.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Fangyuan Wang, Tilong Yang, Ting Wu, Long-Sheng Zheng, Congcong Yin, Yongjie Shi, Xiang-Yu Ye, Gen-Qiang Chen, Xumu Zhang
Summary: A catalytic protocol for the enantio- and diastereoselective reduction of alpha-substituted-beta-keto carbonitriles is described, providing high yields of beta-hydroxy carbonitrile compounds with excellent selectivity. The methodology is suitable for rapid access to pharmaceutical intermediates Ipenoxazone and Tapentadol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Artis Kinens, Simonas Balkaitis, Omar K. Ahmad, David W. Piotrowski, Edgars Suna
Summary: The study presents a non-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols using an isothiourea-derived HyperBTM catalyst and Backvall's ruthenium complex, achieving high enantioselectivities at room temperature. A stereoinduction model based on cation-pi system interactions has been elaborated through DFT calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Soyeon Lee, Do Hyun Ryu, Jaesook Yun
Summary: This study reports the kinetic resolution (KR) and dynamic kinetic resolution (DKR) of gamma-aryl and heteroaryl-substituted butenolides via CuH-catalyzed 1,4-hydroboration. The use of a copper-Ph-BPE catalyst resulted in high selectivity factors for the kinetic resolution of beta-methyl-gamma-phenyl butenolide, and DKR was possible with an amine base (DBU) to obtain highly enantioenriched gamma-butyrolactones (>99% ee) containing beta,gamma-substituents.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Dan Yang, Xiong Wu, Xiao-Jie Zheng, Jian-Hua Xie, Qi-Lin Zhou
Summary: An efficient asymmetric hydrogenation method using a chiral spiro iridium catalyst has been developed to convert racemic gamma-substituted cyclic beta-ketoesters into chiral cyclic beta-hydroxy esters with three stereocenters. The reaction provides high yields (84-97%) with good to excellent enantioselectivities (69->99% ee) and cis,cis-selectivities (up to >99:1).
Article
Chemistry, Multidisciplinary
Ting Chen, Wenjun Liu, Wei Gu, Shengtong Niu, Shouang Lan, Zhifei Zhao, Fan Gong, Jinggong Liu, Shuang Yang, Andrej Emanuel Cotman, Jinshuai Song, Xinqiang Fang
Summary: In this study, a unique dynamic kinetic resolution (DKR) mode was used to achieve the highly selective semi-transfer hydrogenation of unsymmetrical alpha-diketones. The distal carbonyl group was reduced while the proximal carbonyl remained untouched, resulting in the synthesis of enantioenriched acyclic ketones with alpha-hydroxy-alpha'-C(sp2)-functional groups. These products represent a new class of compounds that have not been previously reported. The utility of the synthesized compounds was demonstrated through further transformations, including the rapid synthesis of drug molecules. DFT calculations and control experiments were conducted to gain mechanistic insights into the highly selective semihydrogenation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Kun Wang, Saisai Niu, Xin Guo, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: This research discovers a new method to convert prochiral racemic allylic alcohols to enantioenriched chiral alcohols bearing adjacent stereocenters using a diamine diphosphine Ru complex and tBuOK catalyst. The protocol exhibits a wide substrate scope and high selectivities, and can be applied to the synthesis of enantioenriched chromane and indane compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jianhui Qiao, Wenju Chang, Wenxuan Zhao, Yong Liang, Shaozhong Wang
Summary: A kinetic resolution method has been developed for racemic spiroindolines with s factors <= 15200, allowing the access to enantiomerically enriched indoleannulated medium-sized lactams and spiroindolines through Ir-catalyzed asymmetric allylative ring-opening reaction. Density functional theory calculations support the accurate discrimination of two spiroindoline enantiomers by (eta(3)-allyl)-iridium(III) species and ensure the stereoselective formation of two contiguous stereogenic centers and one axis in the medium-sized lactams.
Article
Chemistry, Organic
Xiaosa Lu, Jie Zhu, Yinhua Huang
Summary: A rhodium-catalyzed highly enantio- and diaster-eoselective alkenylation reaction of Ay-unsaturated butenolides is reported. The use of a chiral diene ligand enables the synthesis of chiral butyrolactones in high yields with extremely high enantioselectivities and high diastereoselectivities. The key process involves the isomerization of butenolides and subsequent dynamic kinetic resolution.
Article
Chemistry, Multidisciplinary
Muxing Zhou, Tatiana Gridneva, Zhenfeng Zhang, Ende He, Yangang Liu, Wanbin Zhang
Summary: This study presents an efficient route for the synthesis of chiral phthalidyl ester prodrugs using a chiral bicyclic imidazole organocatalyst and a continuous injection process. Computational studies suggest a general base catalytic mechanism different from the widely accepted nucleophilic catalytic mechanism. Analysis of key transition states reveals that CH-pi interactions, rather than previously considered cation/pi-pi interactions, play a dominant role in stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yang Zhao, Yi-Xuan Ding, Bo Wu, Yong-Gui Zhou
Summary: Nickel-catalyzed asymmetric hydrogenation was successfully utilized for the kinetic resolution of cyclic N-sulfonylimines derived from [2.2]paracyclophane. High selectivity factors were observed, leading to good yields and high levels of enantiopurity in the recovered materials and hydrogenation products, which are valuable synthetic intermediates for planar chiral [2.2]paracyclophane-based compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
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)
Article
Engineering, Environmental
Mingkai Li, Yingming Wang, Shuzheng Sun, Yanqin Yang, Guoxian Gu, Zisheng Zhang
Summary: Efforts have been made to design novel micro- or nano-structured host materials to trap soluble lithium polysulfides in lithium-sulfur batteries in order to overcome their loss during discharge. Covalent organic framework (COF) materials have shown promise in this regard, with the allyl-rich triazine COF demonstrating high specific capacities and low fading rates, making it a sustainable approach for developing stable and long-lived Li-S batteries.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Organic
Congcong Yin, Yingmin Pan, Xumu Zhang, Qin Yin
Summary: An unprecedented Rh-catalyzed asymmetric and diastereoselective hydrogenation method for easily accessible α,β-disubstituted unsaturated lactams was reported. This method provides synthetically valuable chiral lactams with 1,2-consecutive stereocenters. The reaction can be performed on a gram scale and the products can be transformed into enantiomerically pure trans-3,4-disubstituted piperidines, which are prevalent structural units in medicinal agents.
Article
Chemistry, Organic
Huaxin Yang, Yang Zhou, Zhihan Zhang, Jialin Wen, Xumu Zhang
Summary: We report a convenient method for converting olefins to organic iodides and amines using a specific catalyst, molecular hydrogen, and an electrophilic iodine reagent. High yields and regioselectivities were achieved under mild conditions, and C-N products were obtained through specific workup steps. Control experiments and DFT calculations were conducted to exclude potential reaction pathways.
Article
Chemistry, Physical
Runtong Zhang, Xin Yan, Fanfu Guan, Yu Qian, Jianghua Peng, Jianxin Wang, Baode Ma, Shao-Tao Bai, Jialin Wen, Xumu Zhang
Summary: This article reports the application of a novel tetraphosphite ligand in the ISO-HF of C4 Raffinate. The ligand showed high turnover frequencies and regioselectivities in the reaction, and demonstrated excellent durability in large-scale continuous reactors.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Shaoke Zhang, Rong Zhou, Ya-Nan Duan, Yang Zhou, Xumu Zhang, Jialin Wen
Summary: In this study, a nucleophilic hydrogenation reaction for less electron-rich arenes and heteroarenes was reported. The catalytic activity and electrophilicity of the substrates were analyzed, and a method for synthesizing more challenging substituted benzenes was proposed based on computational modifications of the catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Ke-Qin Wu, Hui Li, Ao Zhou, Wei-Ran Yang, Qin Yin
Summary: A Pd-catalyzed regioselective C-H bond allylic alkylation of phenols with 1,3-dienes is reported, which selectively functionalizes the ortho C-H bond of 2-naphthols, 1-naphthols, and electron-rich phenols to synthesize phenol derivatives with diverse structures. The reaction is accelerated by a diphosphine ligand, does not require any other additive, and exhibits broad substrate scope and good chemo- and regioselectivity. Additionally, an asymmetric variant is investigated, achieving product with up to 55% enantiomeric excess.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Yongjie Shi, Nianxin Rong, Xumu Zhang, Qin Yin
Summary: Chiral primary amines are important in drug synthesis and metal-catalyzed enantioselective reductive amination provides a direct method for their synthesis. However, progress in this field has been slow due to challenges such as reversible formation of unstable intermediates and lack of efficient catalytic systems. While the synthesis of certain substrate types like alpha-keto esters/amides is well-established, enantioselective control in other substrates remains unsolved.
SYNTHESIS-STUTTGART
(2023)
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
Nanoscience & Nanotechnology
Yingming Wang, Mingkai Li, Tianzhuo Wen, Guoxian Gu
Summary: A 3D covalent organic framework (3D COF) with cage-like structures is constructed by interlayer crosslinking of a two-dimensional covalent organic framework (2D COF) with allyl side chain through olefin metathesis reaction. This new material named CAGE-COF has larger specific surface area and more open pore structure than the original 2D COF. The cathode material with CAGE-COF retained 78.7% of its initial capacity after 500 cycles, with a fading rate of 0.04% per cycle.
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, Applied
Lei Xu, Gang Wang, Nianxin Rong, Yang Gu, Le'an Hu, Hengzhi You, Qin Yin
Summary: A one-step and highly enantioselective synthesis of (R)-2-(1-aminoethyl)-4-fluorophenol((R)-I) was developed as a key chiral intermediate for the preparation of the tyrosine kinase inhibitor repotrectinib. The reaction was carried out using a Ru-catalyzed asymmetric reductive amination with NH4OAc as the nitrogen source and H-2 as the reducing agent. The use of a continuous-flow reactor enabled higher reaction efficiency and eliminated the need for column chromatography for product purification, making it a cost-effective alternative strategy for production of repotrectinib.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Materials Science, Multidisciplinary
Tianzhuo Wen, Guoxian Gu, Bofei Wang, Wenjun Zhang, Ruihu Wang
Summary: Abundant cyan broadband emissions are achieved in CsCd(Cl1-yBry)(3) metal halide perovskites (MHPs), addressing the issue of a cyan gap in white light emitting diode (WLED) emission spectrum. Mn2+ ions are doped in CsCd(Cl1-yBry)(3) for yellow supplementation. The resulting single-component white emitter CsCd1-x (Cl1-yBry)(3):xMn(2+) phosphors exhibit a wide band emission, independent cyan and yellow emission peaks, and tunable color temperature.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Dequan Zhang, Jialin Wen, Xumu Zhang
Summary: The construction of chiral quaternary carbon stereocenters has been a long-standing challenge in organic chemistry. In this study, a hydroformylation approach was reported to access chiral quaternary stereogenic centers, and a variety of chiral alpha-quaternary amino acids could be synthesized. The regioselectivity was found to be influenced by the electronic properties of the substituents, and a substrate-catalyst interaction model was proposed based on the chiral environment of the rhodium/Yanphos complex.
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)
