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, Physical
Xue-Song Gu, Ying Xiong, Fan Yang, Na Yu, Pu-Cha Yan, Jian-Hua Xie, Qi-Lin Zhou
Summary: An iridium-catalyzed asymmetric hydrogenation method involving dynamic kinetic resolution was successfully developed using chiral spiro PNN-ligands containing a C5-substituted chiral oxazoline unit. This protocol, combined with simple dehydration, provides a straightforward approach to prepare enantiomerically enriched 3-aryloxy tetrahydrofurans, which are prevalent structural motifs in many approved drugs and clinical candidates.
Article
Chemistry, Multidisciplinary
Wei Zhao, Wenji Wang, Huan Zhou, Qishan Liu, Zhiqing Ma, Haizhou Huang, Mingxin Chang
Summary: A one-pot asymmetric hydrogenation of pyridines with subsequent N-alkylation using a traceless Bronsted acid activation strategy is reported. The reaction exhibits high stereoselectivity and can be used to synthesize indolizidines and quinolizidines. Experimental and theoretical studies reveal that chloride anion and noncovalent interactions play important roles in determining the stereoselectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, 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, 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
Jun Yan, Yu Nie, Feng Gao, Qianjia Yuan, Fang Xie, Wanbin Zhang
Summary: An efficient synthesis of chiral 3-arylindanones was achieved through iridium-catalyzed asymmetric hydrogenation, showing good compatibility with various functional groups and delivering high yields with good enantioselectivities. The reaction was performed on a gram-scale with quantitative yield and the products were easily derivatized into natural products and pharmaceutical agents.
Article
Chemistry, Multidisciplinary
Shasha Zheng, Soumyadeep Chakrabortty, Eszter Barath, Sergey Tin, Johannes G. de Vries
Summary: A new sustainable protocol for the synthesis of bio-derived N-substituted 3-hydroxypyridinium salts from 5-hydroxymethylfurfural using water as a reaction medium is presented. The synthesis of 3-hydroxypyridine, 3-hydroxypyridinium N-oxide, 3-hydroxypiperidine, and a pyridostigmine analogue also highlights the application potentials of this approach.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Zhaofeng Gao, Jingwen Liu, Haizhou Huang, Huiling Geng, Mingxin Chang
Summary: The research reports on efforts to merge two asymmetric reductive amination reactions into a single-step transformation, utilizing specific catalyst and acid additives to successfully synthesize enantiopure secondary amine products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Maria Biosca, Pol de la Cruz-Sanchez, Jorge Faiges, Jessica Margalef, Ernest Salomo, Antoni Riera, Xavier Verdaguer, Joan Ferre, Feliu Maseras, Maria Besora, Oscar Pamies, Montserrat Dieguez
Summary: Ir-MaxPHOX-type catalysts exhibit high catalytic performance in the hydrogenation of a wide range of nonchelating olefins with different geometries, substitution patterns, and degrees of functionalization. These air-stable and readily available catalysts have been successfully used in the asymmetric hydrogenation of di-, tri-, and tetrasubstituted olefins (ee ' s up to 9996). The combination of theoretical calculations and deuterium labeling experiments has revealed the factors responsible for the observed enantioselectivity, allowing for the rationalization of suitable substrates for these Ircatalysts.
Article
Chemistry, Organic
Wen-Bin Cao, Jian-Dong Zhang, Meng-Meng Xu, Hua-Wei Liu, Hai-Yan Li, Xiao-Ping Xu, Shun-Jun Ji
Summary: A catalyst-free [1+2+3] cycloaddition/N-N bond cleavage sequential reaction was developed to access spiroindolines with syn-stereoselectivity by utilizing an underexplored reaction mode of C,N-cyclic azomethine imines. Experimental results and DFT calculations identified peroxide and ethereal solvent as triggers for the reaction, initiating hydrogen abstraction and subsequent N-N bond cleavage.
Article
Chemistry, Applied
David A. Candito, Theodore A. Martinot, Jing Su, Josep Sauri, Yu-hong Lam, Leo A. Joyce, Steven M. Silverman, David L. Sloman, Matthew L. Maddess, Michelle R. Macha
Summary: The synthesis of a key spiroamine building block for medicinal chemistry was achieved through regioselective epoxide ring opening and late-stage Pictet-Spengler reaction, which was quickly optimized using Design of Experiments.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
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
Rong Liu, Mengwei Xia, Cichang Ling, Shaomin Fu, Bo Liu
Summary: This study presents a synthetic approach to the tetracyclic core structure of Dysiherbols A-C. The synthesis involves the intramolecular [2 + 2] cycloaddition to introduce a fused 6/4 ring system, followed by a Pd-catalyzed semipinacol rearrangement/C-sp2-H arylation cascade to construct ring C, and a visible-light-mediated ring-opening of cyclopropyl silyl ether to install the tetracyclic core of Dysiherbols.
Article
Chemistry, Multidisciplinary
Pengju Yang, Guangbin Cheng, Jie Tang, Wei Hu, Guojie Zhang, Hongwei Yang
Summary: 1,2,4-Triazol-3-one (TO) was used as the research object in this paper. A series of TO derivatives were synthesized and characterized, showing excellent thermal stability, low sensitivity, good detonation performance, and positive heats of formation. Compound 6, with high decomposition temperature, low sensitivity, and decent detonation performance, can be used as an insensitive and thermostable energetic material.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Xiaoqing Wang, Yuqing Bai, Xiaoyong Zhai, Bo Wu, Yonggui Zhou
Summary: An environmentally sustainable copper-catalyzed dehydrocoupling polymerization method was developed for efficient preparation of poly(silyl ether)s (PSEs) with high yields and molecular weight. The PSEs exhibit good thermal stability and low glass-transition temperature.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Zhou-Hao Zhu, Yi-Xuan Ding, Yong-Gui Zhou
Summary: A novel transfer-catalyst-free biomimetic reduction method has been developed, which utilizes the chiral and regenerable [2.2]paracyclophane-based NAD(P)H model CYNAM to reduce tetrasubstituted olefins 3-sulfonyl coumarins, resulting in chiral 3-sulfonyl dihydrocoumarins with excellent enantioselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiao-Yong Zhai, Xiao-Qing Wang, Bo Wu, Yong-Gui Zhou
Summary: This study demonstrates a copper-catalyzed enantioselective insertion of carbene into Si-H bond applied to polycondensation, producing a new type of degradable polyesters. Thermogravimetric analysis indicates these polyesters exhibit good thermal stability.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Jie Lin, Zilong Huang, Juan Ma, Bao-Hua Xu, Yong-Gui Zhou, Zhengkun Yu
Summary: Efficient palladium-catalyzed reactions were utilized to synthesize diverse compounds, including trisubstituted 1,3-dienes and tetrasubstituted allenes. The chemo- and regioselectivities were controlled to obtain structurally diverse products.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yunlong Li, Wenchao Jiang, Jie Lin, Juan Ma, Bao-Hua Xu, Yong-Gui Zhou, Zhengkun Yu
Summary: In this study, triple C-H bond activation of aryl enaminones was achieved to access naphtho[1,8-bc]pyrans through oxidative annulation. Depending on the steric and/or electronic environment around the aryl moiety of the enaminones or the electronic impact from the alkynes, 1-naphthols might be formed as the sole products. By using propargyl alcohols as masked terminal alkynes, functionalized but-2-ene-1,4-diones were obtained through rhodium(III)- or rhodium(I)-catalyzed internal alkenyl C-H bond activation. The resulting naphtho[1,8-bc]pyrans exhibited high fluorescence and could be further transformed by chlorination, bromination, and difluoromethylation, demonstrating the potential applicability of the synthetic protocol.
Article
Chemistry, Applied
Zilong Huang, Jie Lin, Juan Ma, Liandi Wang, Yong-Gui Zhou, Zhengkun Yu
Summary: Carbene insertion into C(sp(2))-H bonds of internal alkenes was achieved in air using HFIP as both the mediator and solvent, along with borane B(C6F5)(3) as the catalyst. The reaction showed high yields (47-84%) and broad substituent tolerance, providing an efficient route to synthesize 3-vinylated oxindole and indole derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Xiang Li, Gao-Wei Wang, Li-Xia Liu, Chang-Bin Yu, Yong-Gui Zhou
Summary: Here, the authors describe the first example of palladium-catalyzed asymmetric hydrogenolysis of easily accessible aryl triflates for the construction of axially chiral biaryl scaffolds. The resulting chiral biaryl compounds were used to prepare axially chiral monophosphine ligands, which were further employed in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities and high branched and linear ratios, highlighting the potential utility of this methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tong Niu, Li-Xia Liu, Bo Wu, Yong-Gui Zhou
Summary: A series of [2,2]paracyclophane-based tridentate PNO ligands with planar chirality were designed and synthesized. These easily prepared chiral tridentate PNO ligands were successfully applied to the iridium-catalyzed asymmetric hydrogenation of simple ketones, providing chiral alcohols with high efficiency and excellent enantioselectivities (up to 99% yield and >99% ee). Control experiments demonstrated the indispensability of both N-H and O-H in the ligands.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zilong Huang, Jie Lin, Mingrui Li, Zhengkun Yu, Yong-Gui Zhou
Summary: A zinc(II)-catalyzed [2+2+1] annulation reaction of internal alkenes, diazooxindoles, and isocyanates was developed for the efficient synthesis of multisubstituted spirooxindoles. This multi-component transformation involves the in situ formation of a sulfur-containing spirocyclic intermediate, followed by a 1,3-dipolar addition reaction of the intermediate with the internal alkene, resulting in a formal [2+2+1] annulation in a one-pot manner. The synthetic protocol utilizes a low-toxicity main group metal catalyst, readily available reagents, and provides high yields of up to 96% for the synthesis of multisubstituted spirooxindole derivatives.
Review
Chemistry, Multidisciplinary
Xiao Xiao, Kaini Xu, Zhong-Hua Gao, Zhou-Hao Zhu, Changqing Ye, Baoguo Zhao, Sanzhong Luo, Song Ye, Yong-Gui Zhou, Senmiao Xu, Shou-Fei Zhu, Hongli Bao, Wei Sun, Xiaoming Wang, Kuiling Ding
Summary: Enzymes are essential for biological transformations and have attracted great attention for their structures and functions. Biomimetic chemistry has rapidly developed in response to the demand for bioactive molecules and efficient synthesis. Biomimetic asymmetric catalysis, inspired by enzymes, has been recognized as one of the most promising strategies for producing valuable chiral compounds. This review summarizes the evolution of biomimetic asymmetric catalysis in terms of biomimetic design, catalyst development, and catalytic transformations, providing insights into bridging the gap between bio-catalysis and chemical synthesis.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Zheng Liu, Sheng-Mei Lu, Bao-Qian Zhao, Hao-Dong Chen, Mu-Wang Chen, Yong-Gui Zhou
Summary: A method using zinc chloride was developed to purify compounds with pyridine structure from Mitsunobu reaction mixtures, and a sulfide anion was used to release bipyridines from Ullmann coupling reaction mixtures by competitively coordinating the copper ion. These improvements enabled the facile synthesis of the chiral 2,2'-bipyridine ligand (R-a,S,S)-C3-ACBP, achieving an overall yield of 48% at a 7 gram scale within 3-4 days without column chromatography.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Li-Xia Liu, Yu-Qing Bai, Xiang Li, Chang-Bin Yu, Yong-Gui Zhou
Summary: Combining base-promoted retro-sulfa-Michael addition with palladium-catalyzed asymmetric allenylic alkylation, a streamlined synthesis of chiral thiochromanones containing two central chiralities (including a quaternary stereogenic center) and an axial chirality (allene unit) was successfully achieved, with yields up to 98%, dr of 49.0:1, and >99% ee.
Article
Chemistry, Organic
Wen-Jun Huang, Li-Xia Liu, Yong-Gui Zhou, Bo Wu, Guo-Fang Jiang
Summary: We report a Bronsted acid-catalyzed C6 functionalization of 2,3-disubstituted indoles with 2,2-diarylacetonitriles for efficient construction of cyano-substituted all-carbon quaternary centers with excellent yields. The synthetic utility was demonstrated by the conversion of the cyano-group which enables the divergent preparation of aldehydes, primary amines and amides. Control experiments suggested that this process involves C-H oxidation of 2,2-diarylacetonitriles to in situ generate d,d-disubstituted p-quinone methide intermediates. This protocol provides an efficient method for C6 functionalization of 2,3-disubstituted indoles to construct all-carbon quaternary centers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Yixuan Ding, Yonggui Zhou
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Yuan He, Zilong Huang, Kaikai Wu, Juan Ma, Yong-Gui Zhou, Zhengkun Yu
Summary: C-H functionalization is an effective method for establishing carbon-carbon and carbon-heteroatom bonds, and has made significant progress. Transition-metal-catalyzed carbene insertion to C-H bonds is one of the hot research topics in this field, with various catalyst design strategies and synthetic methods. This review summarizes the research progress up to July 2021 and discusses future directions.
CHEMICAL SOCIETY REVIEWS
(2022)