Article
Chemistry, Organic
Min Gao, Yongyi Li, Xuemin Li, Lin Hu
Summary: A new reaction method has been developed for the direct coupling of simple oxindoles with alkyl dihalides, leading to the synthesis of cyclopentane- and cyclohexane-fused spirooxindole scaffolds with high yields and enantioselectivities. The method utilizes general phase-transfer catalysis and shows broad applicability and mild conditions. It also enables gram-scale synthesis of the core of the drug ubrogepant in two steps.
Article
Chemistry, Multidisciplinary
V. Pratap Reddy Gajulapalli, Nandarapu Kumarswamyreddy, Kanduru Lokesh, Venkitasamy Kesavan
Summary: Utilizing a L-proline derived bifunctional thiourea organocatalyst, a highly functionalized 3,3'-disubstituted oxindole derivatives containing 3-acetyl coumarins and pyranocoumarin fused spirooxindoles can be synthesized with excellent yields (up to 95%) and enantioselectivities (up to 99% ee) in a broad substrate scope.
Article
Chemistry, Organic
Jixin Pian, Qingqing Chen, Yujiao Luo, Zhifei Zhao, Jichang Liu, Lin He, Shi-Wu Li
Summary: An enantioselective cyclopropanation reaction of sulfoxonium ylides with beta,gamma-unsaturated ketoesters catalyzed by a chiral rhodium catalyst has been achieved, leading to the synthesis of various optically pure cyclopropanes.
Article
Chemistry, Organic
Xi-Qiang Hou, Ye Lin, Da-Ming Du
Summary: An efficient asymmetric domino annulation method was developed for the enantioselective construction of functionalized bridged fused ring heterocycles bearing three adjacent stereogenic centers in high yields with excellent diastereo- and enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Shuai-Jiang Liu, Qing Mao, Gu Zhan, Rui Qin, Ben-Hong Chen, Jing Xue, Meng-Lan Luo, Qian Zhao, Bo Han
Summary: The newly designed 3-((2,2,2-trifluoroethyl)amino)indolin-2-ones can be used for the facile synthesis of chiral fluoroalkyl-containing 3,2'-spirooxindole gamma-lactam products with high yields (up to 86%), excellent enantioselectivities (up to 99% ee), and diastereoselectivities (up to >95 : 5 dr) through a secondary amine-catalyzed Michael/hemiaminalization cascade reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Wenyao Wang, Shiqiang Wei, Xiaoze Bao, Shah Nawaz, Jingping Qu, Baomin Wang
Summary: A novel method for the synthesis of optically active spiro[pyrroline-pyrazolones] with various electronic properties has been developed under mild conditions using an organic catalyst derived from a cinchona alkaloid. The protocol provides high yields with good to excellent enantioselectivities.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jindian Duan, Yiyang Mao, Anmei Xian, Binsen Rong, Gaochen Xu, Zhenjiang Li, Lili Zhao, Ning Zhu, Kai Guo
Summary: A copper-catalyzed regioselective [3+2] annulation of malonate-tethered acyl oximes with isatins was developed, providing valuable 2,3-dihydrooxazole-spirooxindoles in moderate to good yields with excellent diastereoselectivity. The reaction involves Cu(I) initiated multiple steps, featuring mild reaction conditions and broad substrate scope. DFT calculations demonstrated that the [3+2] annulation pathway is energetically favorable both in kinetics and thermodynamics.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Xi-Qiang Hou, Jiang-Bo Wen, Li Yan, Da-Ming Du
Summary: The highly efficient cinchona alkaloid-derived squaramide catalyzed reaction successfully synthesizes indanone-derived spiropyrrolidone scaffolds with three contiguous stereocenters, including two spiroquaternary stereocenters, in excellent yields. The protocol provides an economical and practical approach for the asymmetric synthesis of medicinally relevant molecules.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Lona Dutta, Anwita Chattopadhyay, Nisha Yadav, S. S. V. Ramasastry
Summary: This study presents a metal-free strategy for the synthesis of various alpha-arylidene cyclopenta[b]indoles by phosphine-catalysed (3 + 2) annulation of alpha,beta-ynones and 3-nitroindoles. The rearomatisation of the indole nucleus was observed for the first time during this annulative transformation. The method was also applied to the synthesis of an antimalarial natural product, bruceolline E.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Adrian Lavios, Amparo Sanz-Marco, Carlos Vila, M. Carmen Munoz, Jose R. Pedro, Gonzalo Blay
Summary: In this study, the diastereo- and enantioselective dearomative formal [3 + 2] cycloaddition of 2-nitrobenzofurans and alpha-aryl-alpha isocyanoacetate esters successfully produced tricyclic compounds with three consecutive stereogenic centers. The reaction, enabled by a cupreine-ether organocatalyst, exhibited almost complete diastereoselectivity and excellent enantiomeric excesses for various substituted 2-nitrobenzofurans and isocyanoacetates.
Article
Chemistry, Organic
Zhehui Liao, Jiantao Zhang, Tongxiang Cao, Shifa Zhu
Summary: A series of highly strained bicyclo[3.n.1]alkenones have been successfully synthesized with good-to-excellent enantioselectivities and moderate-to-good yields via copper-catalyzed formal [3+3] cycloaddition. The versatile chiral cycloadducts could be selectively converted into various valuable bridge systems, showing great potential for the construction of natural and bioactive compounds containing a [3.n.1] moiety.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xiong-Wei Liu, Zi-Yue Chen, Ren-Ming Liu, Wen-Hui Zhang, Bo-Wen Pan, Jian Zhou, You-Ping Tian, Ying Zhou, Xiong-Li Liu
Summary: Here, we report the use of previously unreported Fischer's base reactants as useful 2C building blocks in (3+2) cycloaddition reactions to construct a library of bispiro[Fischer's base-oxindole] hybrids. These structurally intriguing products, which contain three adjacent quaternary stereocentres, are obtained smoothly with yields up to 82% and >20:1 dr under catalyst-free conditions. Importantly, this study demonstrates for the first time the use of 3-isothiocyanato oxindole as an acceptor and then as a donor in formal (3+2) cycloadditions, providing a practical and straightforward approach to structurally diverse cycloadducts. This work expands the previously limited applicability scope of 3-isothiocyanato oxindoles, which were mainly used as donor/acceptor-based synthons in cycloadditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Hui Xu, Ran Hong, Ming-Yue Weng, Rong-Lu Huang, Guan-Wu Wang, Ze Zhang
Summary: By utilizing different catalysts under different conditions, it is possible to selectively synthesize structurally diverse 4,5'- and 4,4'-imidazolinyl spiropyrazolones, leading to the development of a powerful metal-free method.
Article
Chemistry, Organic
Cidan Lv, Xiangxiang Meng, Min Wang, Yan Zhang, Changwei Hu, Chan Kyung Kim, Zhishan Su
Summary: The mechanism and stereoselectivity of an asymmetric cyclopropanation reaction between 3-alkenyl-oxindole and sulfoxonium ylide catalyzed by a chiral N,N'-dioxide-Mg(II) complex were explored. The presence of N-protecting groups in the isatin enhanced the reactivity of the reactants, while steric effects of substituents in the chiral ligand played a crucial role in the selectivity of the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Pei-Hao Dou, Yan Chen, Yong You, Zhen-Hua Wang, Jian-Qiang Zhao, Ming-Qiang Zhou, Wei-Cheng Yuan
Summary: An organocatalyzed asymmetric dearomative [3+2] annulation reaction of electron-deficient 2-nitrobenzo heteroarenes with 3-isothiocyanato oxindoles was developed, providing access to structurally diverse polycyclic spirooxindoles with three contiguous stereogenic centers in high yields with good diastereo- and enantioselectivities. This organocatalysis protocol offers complementary diastereoselectivity compared to previous work with transition metal catalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Pei-Hao Dou, Shu-Pei Yuan, Yan Chen, Jian-Qiang Zhao, Zhen-Hua Wang, Yong You, Yan-Ping Zhang, Ming-Qiang Zhou, Wei-Cheng Yuan
Summary: In this study, a palladium-catalyzed dearomatization process was developed using either 2-alkylidenetrimethylene carbonates or 2-(hydroxymethyl)-3-arylallyl carbonates to obtain a wide range of indoline-fused tetrahydropyrans in good yields with excellent diastereoselectivities. This reaction demonstrates the first application of pi-allyl palladium 1,4-[O,C]-dipole species in the dearomative cycloaddition of electron-deficient heteroarenes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Li-Wen Shen, Yan-Ping Zhang, Yong You, Jian-Qiang Zhao, Zhen-Hua Wang, Wei-Cheng Yuan
Summary: A highly selective reaction method using inverse electron demand was developed, allowing the formation of diverse compounds in high yields. The reaction involved the interaction between unsaturated thioesters and 1,2,1,3-diazadienes, generated in situ from alpha-halo hydrazones.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhen-Hua Wang, Ji-Hong Liu, Yan-Ping Zhang, Jian-Qiang Zhao, Yong You, Ming-Qiang Zhou, Wen-Yong Han, Wei-Cheng Yuan
Summary: In this study, the enantioselective desymmetrization of N-arylmaleimides was achieved using a Cu(OTf)(2)/chiral ferrocenyl P,N-ligand complex as a catalyst, through the asymmetric 1,3-dipolar cycloaddition reaction of N-2,2,2-trifluoroethylisatin ketimines. A series of structurally diverse F3C-containing octahydropyrrolo[3,4-c]pyrroles, bearing four contiguous carbon stereocenters and one stereogenic chiral C-N axial bond, were obtained with excellent results (<= 99% yield, >20:1 dr, and 99% ee).
Article
Chemistry, Organic
Ting -Ting Li, Yong You, Ting-Jia Sun, Yan-Ping Zhang, Jian-Qiang Zhao, Zhen-Hua Wang, Wei-Cheng Yuan
Summary: A copper-catalyzed decarboxylative cascade cyclization of propargylic cyclic carbonates/carbamates with pyridinium 1,4-zwitterionic thiolates is developed, resulting in the efficient embedding of four new bonds (two C-C, one C-O/N, one C-S) and four new stereocenters into tetracyclic fused scaffolds in a single step, with moderate to good yields and excellent diastereoselectivities.
Article
Chemistry, Organic
Wei-Cheng Yuan, Lei Yang, Jian-Qiang Zhao, Hong-Yan Du, Zhen-Hua Wang, Yong You, Yan-Ping Zhang, Jiabin Liu, Wenjing Zhang, Ming-Qiang Zhou
Summary: A copper-catalyzed reaction of N-2,2,2-trifluoroethylisatin ketimines with benzo[b]thiophene sulfones was developed for the enantioselective 1,3-dipolar cycloaddition. The reaction afforded pentacyclic spirooxindoles containing pyrrolidine and benzo[b]sulfolane subunits in high efficiency and with excellent selectivity under mild conditions.
Article
Chemistry, Organic
Yong You, Ting-Ting Li, Ting-Jia Sun, Yan-Ping Zhang, Zhen-Hua Wang, Jian-Qiang Zhao, Wei-Cheng Yuan
Summary: A copper-catalyzed asymmetric decarboxylative propargylic substitution method was developed for the synthesis of compounds with vicinal quaternary-tetrasubstituted carbon stereo centers.
Article
Chemistry, Organic
Shun Zhou, Hui-Ling Qian, Jian-Qiang Zhao, Yong You, Zhen-Hua Wang, Jun-Qing Yin, Yan-Ping Zhang, Ming-Feng Chen, Wei-Cheng Yuan
Summary: A formal [4 + 2] cycloaddition reaction between 3-nitroindoles and ortho-aminophenyl p-quinone methides was developed through a dearomatization process. This method provides an efficient approach for the synthesis of tetrahydro-5H-indolo[2,3-b]quinolones with satisfactory results. The use of bifunctional Cinchona alkaloid-squaramide as the catalyst enabled the asymmetric version of the reaction, leading to the formation of chiral products with moderate to good enantioselectivities. This work represents the first dearomative cycloaddition of electron-deficient heteroarenes triggered by aza-Michael addition from p-QMs.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Zhen-Hua Wang, Tong Zhang, Li-Wen Shen, Xiu Yang, Yan-Ping Zhang, Yong You, Jian-Qiang Zhao, Wei-Cheng Yuan
Summary: Cycloaddition reactions between heteroaromatic N-ylides and electron-deficient olefins have been developed. The N-ylides, generated in situ from N-phenacylbenzothiazolium bromides, react smoothly with maleimides under mild conditions to yield fused polycyclic octahydropyrrolo[3,4-c]pyrroles in high yields. This reaction concept can also be extended to 3-trifluoroethylidene oxindoles and benzylidenemalononitriles, enabling the synthesis of highly functionalized polyheterocyclic compounds. A gram-scale experiment was carried out to demonstrate the practicality of the methodology.
Article
Biochemistry & Molecular Biology
Jun-Qing Yin, Yan-Ping Zhang, Yong You, Zhen-Hua Wang, Jian-Qiang Zhao, Qing Peng
Summary: In this study, DFT calculations were used to explore the properties of iron-silicon interface structures and found that the strong Fe-Si interaction affected the application of magnetic materials based on reconstructed Si surface.
Article
Biochemistry & Molecular Biology
Jian-Qiang Zhao, Wen-Jie Wang, Shun Zhou, Qi-Lin Xiao, Xi-Sha Xue, Yan-Ping Zhang, Yong You, Zhen-Hua Wang, Wei-Cheng Yuan
Summary: An unprecedented N-alkylation of 3-nitroindoles with para-quinone methides was developed for the first time. Using potassium carbonate as the base, a wide range of structurally diverse N-diarylmethylindole derivatives were obtained with moderated to good yields via the protection group migration/aza-1,6-Michael addition sequences. The reaction process was also demonstrated by control experiments.
Article
Biochemistry & Molecular Biology
Lin-Qiang Li, Jian-Qiang Zhao, Yan-Ping Zhang, Yong You, Zhen-Hua Wang, Zhen-Zhen Ge, Ming-Qiang Zhou, Wei-Cheng Yuan
Summary: In this research, a metal-free diastereoselective formal 1,3-dipolar cycloaddition reaction was developed for the desymmetrization of cyclopentene-1,3-diones using N-2,2,2-trifluoroethylisatin ketimines. The reaction efficiently leads to the formation of tetracyclic spirooxindoles containing pyrrolidine and cyclopentane subunits with good yields and diastereoselectivities. The methodology was also extended to trifluoromethyl-substituted iminomalonate, resulting in the formation of bicyclic heterocycles with fused pyrrolidine and cyclopentane moieties in moderate yields and high diastereoselectivities.
Article
Chemistry, Organic
Zhen-Hua Wang, Tong Zhang, Qing-Fei Yan, Jian-Qiang Zhao, Yong You, Yan-Ping Zhang, Jun-Qing Yin, Wei-Cheng Yuan
Summary: In this article, various α-aryl vinylsulfonium salts were successfully transformed under mild reaction conditions, leading to the synthesis of diverse 1,2-dihydroquinoline and ring-fused tetrahydroquinoline skeletons with moderate to excellent yields. The potential application of the method was demonstrated by scale-up experiments and further derivatizations of the products. The developed protocol offers mild and transition-metal-free reaction conditions, along with easy operation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Yong You, Yan-Ping Zhang, Zhen-Hua Wang, Jian-Qiang Zhao, Jun-Qing Yin, Wei-Cheng Yuan
Summary: Copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates are an efficient way to construct various useful skeletons. The field has gained attention and made significant progress due to the reaction sites of propargylic cyclic carbonates/carbamates and the advantages of copper catalysis. This review addresses the achievements, mechanisms, synthetic applications, limitations, challenges, and opportunities in this field.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Organic
Zhen-Hua Wang, Yong You, Jian-Qiang Zhao, Yan-Ping Zhang, Jun-Qing Yin, Wei-Cheng Yuan
Summary: In conjugated pi systems, suitable strategies can generate pi-extended enolates from pronucleophiles and these tend to undergo stereoselective vinylogous reactions for remote functionalization. However, bench-stable unsaturated pronucleophiles have historically lacked proximal functionalization. Recent development of synthetic methods and catalytic systems have addressed this issue. This review highlights the achievements, mechanism insights, and challenges in the proximal functionalization of unsaturated pronucleophiles.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yong You, Guo-Ying Gan, Si-Yang Duan, Yan-Ping Zhang, Qun Li, Zhen-Hua Wang, Jian-Qiang Zhao, Xiong-Li Liu, Wei-Cheng Yuan
Summary: A highly enantioselective aza-Friedel-Crafts reaction was established for the synthesis of chiral tryptanthrin derivatives using chiral phosphoric acid as a catalyst. The synthesized compounds exhibited excellent yields and good to excellent enantioselectivities, and showed potential for medicinal applications, particularly in the treatment of leukemia.
ORGANIC CHEMISTRY FRONTIERS
(2023)
