Review
Chemistry, Multidisciplinary
Kuntal Pal, Chandra M. R. Volla
Summary: Alpha-imino carbenoids generated via transition metal catalyzed denitrogenative ring-opening of N-sulfonyl-1,2,3-triazoles have found extensive applications in synthetic organic chemistry over the past decade. In addition, 3-diazoindolin-2-imines have been successfully used as alternative sources of alpha-imino carbenoid precursors for the development of methodologies to access diverse indole derivatives. This review summarizes the insertion reactions of alpha-imino metal carbenes derived from N-sulfonyl-1,2,3-triazoles and 3-diazoindolin-2-imines.
Article
Chemistry, Organic
Fei Zhao, Xin Gong, Yangbin Lu, Jin Qiao, Xiuwen Jia, Hangcheng Ni, Xiaowei Wu, Xiaoning Zhang
Summary: This method reports the controlled divergent synthesis of tetrasubstituted 1,3-enynes and alkynylated 3H-pyrrolo[1,2-a]indol-3-ones through rhodium-catalyzed reactions, featuring excellent selectivity, broad substrate scope, moderate to high yields, and good functional group compatibility under mild redox-neutral conditions.
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Kuiyong Dong, Mengting Liu, Xinfang Xu
Summary: This review summarizes the applications of copper as a catalyst in synthetic chemistry and catalysis. It focuses on the reactions between copper carbene intermediates and alkyne species. Two different reaction models are discussed, highlighting the practicality and mildness of these methods.
Article
Chemistry, Physical
Xinyu Zhang, Paramasivam Sivaguru, Giuseppe Zanoni, Xinyue Han, Minghui Tong, Xihe Bi
Summary: This study reports a novel enantioselective synthesis method, which enables the efficient synthesis of chiral fluoroalkyl derivatives by using fluoroalkyl N-triftosylhydrazones as the carbene source under mild conditions.
Article
Chemistry, Applied
Fei Zhao, Jing Chen, Jin Qiao, Yangbin Lu, Xiaoning Zhang, Hui Mao, Shiyao Lu, Xin Gong, Siyu Liu, Xiaowei Wu, Long Dai
Summary: This study achieved the synthesis of functionalized 1H-imidazo[1,5-a]indol-3(2H)-ones by utilizing electron-deficient alkynes as unconventional C-1 synthons in a redox-neutral rhodium(III)-catalyzed [4+1] annulation. The process exhibited high chemo- and regioselectivity, broad substrate scope, good tolerance of functional groups, moderate to high yields, and mild redox-neutral conditions, providing a robust method to access valuable 1H-imidazo[1,5-a]indol-3(2H)-ones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Yuncan Chen, Shan Lv, Ruizhi Lai, Yingying Xu, Xin Huang, Jianglian Li, Guanghui Lv, Yong Wu
Summary: This study demonstrates the efficient coupling of sulfoxonium ylides with thioureas under rhodium catalysis to produce 2-aminothiazoles with good functional group tolerance. This approach provides a convenient method for accessing a variety of 2-aminothiazole derivatives with high chemoselectivity.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
Jianwen Jin, Andres Felipe Leon Rojas, Yichao Zhao, Sara Helen Kyne, Bo Xia, Bingwei Zhong, Philip Wai Hong Chan
Summary: This study presents a synthetic method for efficiently preparing (E)-3-arylazoindoles, which does not require the exclusion of air or moisture and can be conducted under mild reaction conditions. The suggested mechanistic pathway of the azo coupling reaction reveals the unique electrophilic behavior of α-diazocarbonyl compounds. Experimental studies provide insights into the preferential generation of a (1H-indol-3-yl)gold species and its impact on the regio- and chemoselectivity of the products. The utility of this synthetic method has been demonstrated in the synthesis of specific molecules, molecular switch assembly, and late-stage functionalization of biologically relevant molecules.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Kotaro Yamashita, Kota Sato, Yutaka Tanji, Jun-ya Hasegawa, Tetsuaki Fujihara
Summary: Dirhodium complexes with bulky carboxylate ligands were synthesized and characterized. The steric bulk of carboxylate ligands has an impact on the selectivity in Rh-catalyzed intramolecular reactions: Rh catalysts with bulky carboxylate ligands preferentially produced five-membered ring products via insertion into a carbon-hydrogen bond, while conventional Rh catalysts obtained six-membered ring products via insertion of a carbon-carbon double bond.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Lianfen Chen, Chaoyi Zhao, Weixian Mo, Chunsheng Li, Xiaoming Lin
Summary: A facile and efficient methodology using a dirhodium metal-organic cage as a heterogeneous catalyst was demonstrated for the generation of C-X (X = Si, B) bond through a carbene insertion process. Functionalized alkynes served as safe carbene precursors and yielded Si-H and B-H insertion products in moderate to excellent yields. The reactions showed high atom-economy, broad substrate scope, and mild reaction conditions. The MOC-Rh-1 catalyst could be easily recovered and reused without significant loss in activity.
Article
Chemistry, Multidisciplinary
Nikita M. Ankudinov, Denis A. Chusov, Yulia Nelyubina, Dmitry S. Perekalin
Summary: A new method for synthesizing chiral diene rhodium catalysts has been introduced, with one catalyst showing efficient asymmetric insertion of diazoesters into B-H and Si-H bonds with high yields and enantiomeric purity. The stereoselectivity of separation and catalytic reaction can be predicted by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Igor Yu Grishin, Nikolai A. Arutiunov, Dmitrii A. Aksenov, Nicolai A. Aksenov, Alexander Aksenov, Amina Z. Gasanova, Elena A. Sorokina, Carolyn Lower, Michael Rubin
Summary: In this study, polyphosphoric acid was used as a catalyst to efficiently synthesize 3-(1H-indol-3-yl)benzofuran-2(3H)-ones via condensation reaction between 3-(2-nitrovinyl)-1H-indoles and phenols.
Article
Chemistry, Physical
Jie Chen, Jiabin Han, Jian Zhang, Ling Li, Zhengyu Zhang, Yanhui Yang, Yaojia Jiang
Summary: In this study, we describe an efficient amine/Rh(II) dual catalytic system that enables the reassembly of conjugated alkynes with cyclopropenes, resulting in the construction of alpha-vinyldicarbonyl derivatives under mild reaction conditions. This cascade platform offers high atom and step economies, and is compatible with a broad range of substrates including complex natural and unnatural molecules for late-stage functionalization.
Article
Chemistry, Multidisciplinary
Wei Yang, Maoping Pu, Xiaobin Lin, Min Chen, Yanji Song, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: In this study, a novel method was developed for the synthesis of vinyl gamma-amino amides with high gamma-selectivity and enantioselectivity using a high-spin chiral complex catalyst. The calculation showed a spin state change from quartet cobalt(II) complex to doublet Co(II)-carbene species for Z-selective and enantioselective nucleophilic addition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Cheng Li, Bin Zhao, Guojiang Mao, Guo-Jun Deng
Summary: We developed a redox-neutral synthesis of indenones catalyzed by rhodium(III), which does not require harsh conditions or any external oxidants. Mechanistic experiments and DFT calculation revealed that the reaction involves various cascade processes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Biochemistry & Molecular Biology
Jiuling Li, Dong Xing, Wenhao Hu
Summary: An efficient synthesis method for alpha-halo-alpha-arylseleno ketones has been developed through gem-difunctionalization of alpha-diazoarylketones with diaryldiselenides and N-halosuccinimides. A series of products were obtained in excellent yields and chemoselectivities under mild conditions. The transformation is proposed to occur via the generation of a key intermediate arylselenenyl halide from diaryldiselenides/N-halosuccinimides, followed by addition with alpha-diazoarylketones to form the desired gem-difunctionalization products.
MOLECULAR DIVERSITY
(2021)
Article
Chemistry, Organic
Farrukh Sajjad, Alavala Gopi Krishna Reddy, Dong Xing, Suzhen Dong, Wenhao Hu
Summary: An unprecedented synthetic route towards a variety of 3-anilino-1H-indoles has been achieved through a domino ruthenium-catalyzed annulation and subsequent iron-promoted fragmentation and rearrangement. The strategy is applicable to deliver diversely substituted indole esters, with compound 4i exhibiting the best inhibitory activity with an IC50 value of 0.05 mu M, paving the way for the discovery of promising lead compounds in the future.
Article
Chemistry, Multidisciplinary
Guizhi Dong, Ming Bao, Xiongda Xie, Shikun Jia, Wenhao Hu, Xinfang Xu
Summary: The study presents an unprecedented catalytic asymmetric allylation of isatins and isatin-derived ketimines via a gold and chiral organocatalyst cooperative catalysis strategy, leading to the expeditious synthesis of chiral 2,5-disubstituted alkylideneoxazolines with vicinal stereogenic centers. The mechanism involves an alkylgold intermediate, and the X-ray crystal structure of the allylgold species reveals its unique stability and reactivity. Additionally, an asymmetric formal hetero-ene reaction of the gold intermediate is enabled with the assistance of a quinine-derived squaramide catalyst, extending the synthetic applications of gold complexes and the versatility of gold catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ming Bao, Jinzhou Chen, Chao Pei, Sujie Zhang, Jinping Lei, Wenhao Hu, Xinfang Xu
Summary: An unprecedented gold-catalyzed ketene C=O/C=C bifunctionalization method has been developed, initiated by gold-catalyzed Wolff rearrangement of diazoketone to form the ketene intermediate, followed by nucleophilic addition and terminated with two divergent cyclization processes. Depending on the nucleophiles used, different cyclization pathways are observed, leading to the formation of different products, providing a novel reaction pattern for the ketene dual functionalization.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Applied
Ming Bao, Xiongda Xie, Wenhao Hu, Xinfang Xu
Summary: A gold-catalyzed carbocyclization/C=N bond formation cascade reaction has been developed for the synthesis of polyfunctionalized 4-iminonaphthalenones and indenes in good to high yields under mild reaction conditions. The resulting products could be converted into multi-substituted 2-naphthol derivatives in high yields.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Kemiao Hong, Shanliang Dong, Xinxin Xu, Zhijing Zhang, Taoda Shi, Haoxuan Yuan, Xinfang Xu, Wenhao Hu
Summary: An enantioselective intermolecular Mannich-type interception of phenolic oxonium ylides with imines has been developed using cooperative catalysis with achiral dirhodium complex and chiral phosphoric acid. The synthesis of enantioenriched 2,2-disubstituted dihydrobenzofurans with good to high yield and high to excellent enantioselectivity under mild conditions was achieved. Preliminary antitumor activity study showed high anticancer potency of the reduction product 7 against human lung adenocarcinoma cells (A549 cells, IC50 = 9.13 mu M).
Article
Chemistry, Multidisciplinary
Zhenghui Kang, Wenju Chang, Xue Tian, Xiang Fu, Wenxuan Zhao, Xinfang Xu, Yong Liang, Wenhao Hu
Summary: The study presents a novel asymmetric allylation reaction through ternary cooperative catalysis, enabling the expedient access to chiral alpha,alpha-disubstituted ketones with high enantioselectivity. Experimental and computational studies have elucidated the mechanism and origin of enantioselectivity in this three-component reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xiangrong Liu, Xue Tian, Jiawu Huang, Yu Qian, Xinfang Xu, Zhenghui Kang, Wenhao Hu
Summary: An enantioselective three-component reaction of alpha-propargylic-3-indolymethanol with diazoindolinone and alcohol has been achieved under the cocatalysis of Rh(II) and chiral phosphoric acid (CPA). The reaction proceeds through regio- and enantiospecific addition of an in situ formed oxonium ylide to the alpha-propargylic indole iminium ion, providing an efficient access to chiral propargylic indole derivatives with high yields and enantioselectivities.
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Chemistry, Organic
Xiang Fu, Jie Tang, Ruyu Hua, Xiaoqian Li, Zhenghui Kang, Huang Qiu, Wenhao Hu
Summary: This study reports two DNA-compatible reactions with alkenes and diazo compounds, providing hydroalkylation and cyclopropanation products in moderate to excellent yields. These transformations not only offer new access to C(sp3)-C(sp3) bond formation in DELs with excellent functional group tolerance, but also represent practical ligation methods to introduce functionalized molecules into DNA.
Article
Chemistry, Organic
Su Zhou, Qianqian Liu, Ming Bao, Jie Huang, Junjian Wang, Wenhao Hu, Xinfang Xu
Summary: A new synthesis method for 2-indolyl indolone N-oxides via gold(i)-catalyzed cascade reaction of o-nitroalkynes with indoles has been developed, leading to highly efficient conversion into 2-indolylbenzoxazinone with strong blue fluorescence. The synthesized compounds were also evaluated for their antitumor activity in small cell lung cancer, with compounds 3d and 4s showing high anticancer potency against SCLC cells.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Kai Zhou, Ming Bao, Hongkai Sha, Guizhi Dong, Kemiao Hong, Xinfang Xu, Wenhao Hu
Summary: A Rh-catalyzed diastereoselective three-component reaction has been developed for the efficient synthesis of vicinal diamine derivatives with two tertiary stereocenters in high yields (75%->95%) and high to excellent diastereoselectivities. The generated product can be easily converted to free diamines via hydrolysis of the imine motif under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Farrukh Sajjad, Yanmei Chen, Xue Tian, Suzhen Dong, Alavala Gopi Krishna Reddy, Wenhao Hu, Dong Xing
Summary: An efficient strategy for the construction of 1,4-oxazines from simple alpha-amino ketones and diazo pyruvates catalyzed by RuCl3 was reported, showing promising anticancer activities towards HCT116. This transformation involves a tandem N-H insertion/cyclization sequence via an enol formation under mild reaction conditions with broad functional group tolerance.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Medicine, Research & Experimental
Qiyao Zheng, Hui Dong, Jianshan Mo, Yi Zhang, Jie Huang, Shumin Ouyang, Shuo Shi, Kai Zhu, Xinming Qu, Wenhao Hu, Peiqing Liu, Yuanxiang Wang, Xiaolei Zhang
Summary: Constitutive activation of STAT3 is common in NSCLC and plays a crucial role in cancer progression and acquired resistance to targeted therapies. W2014-S, a novel STAT3 inhibitor, demonstrated significant anti-tumor activities by disrupting STAT3 signaling and sensitizing resistant NSCLC cells to EGFR-TKIs in vitro and in vivo. Combining W2014-S with gefitinib could be a promising strategy to overcome EGFR-TKIs acquired resistance in NSCLC patients.
Article
Chemistry, Organic
Jiuling Li, Bin Li, Juan Chen, Xinyu Jia, Min Wang, Chengjun Hao, Xinhua Zheng, Hongmei Dai, Wenhao Hu
Summary: A series of gem-chlorosulfurization products bearing difluoromethyl substituents were synthesized directly from p-toluenesulfonyl difluorodiazoethane (TsCF2CHN2), disulfides, and PhICl2 in high to excellent yields without the need for any catalysts or additives. The products showed high functional group compatibility and could be efficiently converted to sulfur-containing and aryl substituted difluoromethyl derivatives through a feasible multi-component operation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
