Article
Chemistry, Organic
Subhendu Pramanik, Sarat Chatterjee, Rumjhum Banerjee, Chinmay Chowdhury
Summary: This study presents a direct synthesis method for carbazoles containing aryl and aryl ketone groups. The reaction involves Pd(II)-catalyzed cascade reactions, which enables the fast assembly of carbazoles through four carbon-carbon bond formations. The absence of aldehyde substrates leads to the formation of C4-aryl-substituted carbazoles. The method is versatile for the synthesis of biscarbazole derivatives.
Article
Chemistry, Applied
Fang Fang, Haolin Zheng, Weipeng Li, Guojiang Mao, Shanping Chen, Guo-Jun Deng
Summary: A metal- and solvent-free strategy for the preparation of maleimide-fused carbazoles has been developed, starting from 2-(indol-3-yl)cyclohexanones and maleimides. This approach was catalyzed by trimethylsulfoxonium iodide and involved a cascade of oxidation, [4+2] annulation, and dehydrogenative aromatization, providing various maleimide-fused carbazoles in 45-90% yields. Moreover, these products could be further transformed into other polycyclic aromatic hydrocarbons.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Zhidong Jiang, Jianhui Zhou, Haoran Zhu, Hong Liu, Yu Zhou
Summary: A novel Rh(III)-catalyzed C-H activation/annulation cascade of indole-enaminones with diazo compounds was reported, generating diversely functionalized carbazole frameworks with good to excellent yields. The most notable feature is the formation of a novel [5 + 1] cyclization product, accompanied by the complete removal of acetyl and N,N-dimethyl groups from the substrates, rather than the expected [4 + 2] cyclization products.
Article
Chemistry, Organic
Minghui Qi, Muhammad Suleman, Jianwei Xie, Ping Lu, Yanguang Wang
Summary: We report a simple and efficient method for the selective C-H bond insertion of copper carbenes generated in situ from 4-diazo-1,4-dihydroisoquinolin-3-ones into beta-C(sp(2))-H bonds of N-sulfonyl enamides. This reaction yields a series of 4-(1,4,5,6-tetrahydropyridin-3-yl)-1,4-dihydroisoquinolin-3(2H)-ones with good to excellent yields. The reaction benefits from its simple and mild reaction conditions, the use of a cheap catalyst, readily accessible starting materials, and a broad substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Hongmei Zhu, Lei Chen, Rongxian Bai, Yanlong Gu
Summary: Two classes of indole-tetrahydropyridine hybrid molecules were synthesized via three-component reactions, providing a straightforward approach for accessing diverse molecular structures. The reactions were likely triggered by Michael addition, leading to the formation of indol-3-ylimine intermediate, which was then trapped by the indole component. The resulting indol-3-yl-substituted tetrahydropyridines could be converted into indole-pyridine hybrid molecules with the aid of DDQ.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Chunhua Ma, Yue Wang, Guang Chen, Jingyi Li, Yuqin Jiang, Xinying Zhang, Xuesen Fan
Summary: This paper presents the synthesis of 3-(indol-2-yl)succinimide/maleimide and indoyl/pyrrolyl fused benzodiazepine skeletons through the reaction of 2-(1H-indol-1-yl)anilines with maleimides. Mechanistic studies reveal that the formation of these compounds involves Ru(ii)-catalyzed and free amino group-assisted regioselective bond cleavage and coordination reactions. The synthesized compounds show potential as lead compounds for the development of anticancer drugs.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Wen-Bi Hu, Yan-Qing Qiu, Wen-Yi Wei, Qing Li, Yan-Jun Xu
Summary: In this study, novel complex C2-quaternary-indol-3-one units bearing versatile nitro groups were successfully developed from pseudo-indolones and alpha,beta-unsaturated nitroolefins through rhodium-catalyzed C-H activation/[3 + 2] spirocyclization. Notably, four diastereomers could be selectively obtained in the reaction by condition control.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Furen Zhang, Chunmei Li, Zhen Yang, Linjun Shao, Chenze Qi, Zhenlu Shen
Summary: A solid acid-catalyzed cascade reaction has been developed to rapidly construct complex polysubstituted indole compounds. This method has the advantages of low cost, wide substrate scope, and recyclable catalyst.
Article
Chemistry, Organic
Yuan Zhang, Tongda Liu, Li Liu, Haiyang Guo, Heyang Zeng, Wei Bi, Guanyinsheng Qiu, Wei Gao, Xin Ran, Long Yang, Guanben Du, Lianpeng Zhang
Summary: A novel and facile protocol for the synthesis of benz[c,d]indol-2-imines was reported, which involves palladium-catalyzed C-C and C-N coupling reactions of 8-halo-1-naphthylamines with isocyanides in a single step. The reaction exhibits broad substrate scopes and mild conditions, providing an efficient alternative for the construction of antiproliferative agents and BET bromodomain inhibitors.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Lin Lu, Zuoliang Zheng, Yongjie Yang, Bo Liu, Biaolin Yin
Summary: Polycyclic indolines and indolenines were synthesized via base-catalyzed intramolecular dearomatizing 3-alkenylation reactions of alkynyl indoles at room temperature. The base enhanced the nucleophilicity of the carbon at the 3-position of the indole moiety, facilitating an exclusive 5-exo-dig cyclization reaction with the alkyne to form spiroindolenines. The imine functionality of the spiroindolenines could undergo in situ nucleophilic addition to form spiroindolines when R was a carbamoyl group or reduction to form spiroindolines when R was H.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Applied
Fernando Martinez-Lara, Anisley Suarez, Noelia Velasco, Samuel Suarez-Pantiga, Roberto Sanz
Summary: The gold-catalyzed transformation of propargylic glycols with thiols results in the formation of alpha-indol-3-yl alpha-((Z)-2-thioalkenyl) ketones through a complex but selective reaction mechanism. This sequence involves regioselective thiolation of indolyl diols followed by the attack of sulfur on the activated alkyne, rather than the indole. The final compounds are obtained in high yields from simple starting materials such as indolyl acyloins, ethynyl magnesium bromide, and thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
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, Applied
Mariyaraj Arockiaraj, Gargi Singh, Sasi Sree Marupalli, Venkatachalam Rajeshkumar
Summary: A visible-light-induced, metal-free, base-free, and photocatalyst-free protocol for the efficient synthesis of tryptanthrin and its derivatives has been developed. The reaction is compatible with a wide range of substrates and exhibits good to high yields. Furthermore, a novel synthetic transformation of tryptanthrin derivatives was achieved through decarboxylative addition of cyanoacetic acid for the first time, without the need for an external photocatalyst.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jing Sun, Chen Yan, Qiu Sun, Ying Han, Chao-Guo Yan
Summary: In chloroform, the p-TsOH promoted annulation reaction of 3-(indol-3-yl)maleimides and (indol-2-yl)diphenylmethanols resulted in functionalized pyrrolo[3 ',4 ':6,7]cyclohepta[1,2-b:4,5-b ']diindoles with satisfactory yields, demonstrating a formal [4+3] cycloaddition and an unprecedented rearrangement of the maleimide motif. Alternatively, the reaction of 3-(indol-3-yl)maleimides and 3-hydroxy-3-(indol-3-yl)-indolin-2-ones in acetonitrile produced functionalized spiro[indoline-3,9 '-pyrrolo[3 ',4 ':4,5]cyclopenta[1,2-b]indole] in good yields and with high diastereoselectivity. On the other hand, the p-TsOH promoted reaction of 3-(indol-3-yl)maleimides and 2-hydroxy-2-(indol-3-yl)-indene-1,3-diones yielded functionalized spiro[indene-2,9 '-pyrrolo[3 ',4 ':4,5]cyclopenta[1,2-b]indoles] as major products and spiro[indene-2,9 '-pyrrolo[3 ',4 ':6,7]cyclohepta[1,2-b:4,5-b ']diindoles] as minor products.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Sima Alavi, Jian-Bin Lin, Huck K. Grover
Summary: The study investigates the rearrangement of indolyl alpha-diazocarbonyl compounds under metal catalysis, and reveals the effects of catalyst and substituents on the selectivity of the rearrangement process.
Article
Chemistry, Multidisciplinary
Sheng Xu, Herong Chen, Zhijun Zhou, Wangqing Kong
Summary: Catalytic alkene difunctionalization using decatungstate photo-HAT and nickel catalysis allows for the direct activation of aliphatic C-H bonds, enabling the installation of highly functionalized C(sp(3))-hybrid centers. This strategy demonstrates practicality in selective late-stage functionalization of natural products and concise synthesis of pharmaceutically relevant molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yate Chen, Zhengtian Ding, Yiming Wang, Wenfeng Liu, Wangqing Kong
Summary: This study describes an unprecedented nickel-catalyzed domino reductive cyclization of alkynes and o-bromoaryl aldehydes, providing straightforward access to biologically significant indanones and spiroindanone pyrrolidine derivatives in good yields with excellent regio- and diastereoselectivity. Preliminary mechanistic studies suggest that indanones are formed through cyclization of o-bromoaryl aldehydes and alkynes to form indenol intermediates, followed by hydrogen autotransfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhengtian Ding, Yiming Wang, Wenfeng Liu, Yate Chen, Wangqing Kong
Summary: The study presents an unprecedented nickel-catalyzed one-pot synthesis of enantioenriched spiroindanones from readily available 1,6-enynes and o-formylarylboronic acids. The reaction proceeds smoothly under redox-neutral conditions, demonstrating excellent regio-, enantio-, and diastereoselectivity with a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiao-Wang Chen, Jun-Ping Yue, Kuai Wang, Yong-Yuan Gui, Ya-Nan Niu, Jie Liu, Chuan-Kun Ran, Wangqing Kong, Wen-Jun Zhou, Da-Gang Yu
Summary: The asymmetric reductive carbo-carboxylation of alkenes via nickel catalysis provides an efficient method for the synthesis of carboxylic acids with mild reaction conditions, wide substrate scope, and good selectivity. This approach opens up a new avenue for the total synthesis of chiral natural products using CO2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Qi Pan, Yuanyuan Ping, Yifan Wang, Ya Guo, Wangqing Kong
Summary: This study presents a catalyst-controlled dicarbofunctionalization of alkenes for the synthesis of five- and six-membered benzo-fused lactams bearing all-carbon quaternary centers. Different regioselectivity patterns can be achieved by using chiral bidentate ligands, resulting in high yields and excellent enantioselectivities. The synthetic value of this regiodivergent protocol is demonstrated by the preparation of biologically relevant molecules and structural scaffolds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Hengxu Li, Jiachang Chen, Jueqi Dong, Wangqing Kong
Summary: A Ni-catalyzed reductive arylcyanation of alkene using an environmentally benign and nontoxic organo cyanating reagent has been developed. This method allows for the rapid synthesis of cyanosubstituted oxindoles and isoquinoline-1,3-diones with high functional group tolerance, and also features an enantioselective version for the construction of enantiomerically enriched 3-cyanomethyl oxindoles. Additionally, this approach has been successfully applied to the synthesis of natural alkaloids (+)-esermethole and (+)-physostigmine.
Article
Chemistry, Multidisciplinary
Yuanyuan Ping, Xiao Li, Qi Pan, Wangqing Kong
Summary: Ligand-directed divergent synthesis is a strategy that can transform common starting materials into distinct molecular scaffolds. This strategy enables the rapid construction of structurally rich collection of small molecules for biological evaluation and reveals novel modes of catalytic transformation, representing one of the most sought-after challenges in synthetic chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yuanyuan Ping, Qi Pan, Ya Guo, Yongli Liu, Xiao Li, Minyan Wang, Wangqing Kong
Summary: Switchable selectivity in skeletal rearrangement can be achieved by controlling the migratory aptitude of different groups. Modifying the ligands on the metal catalyst and changing the oxidation states of the metal allow control over the migratory ability. This method enables site-selective activation and reorganization of C-C bonds and has been used for the synthesis of fluorine-containing scaffolds with medicinal relevance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Teng Ma, Xiao Li, Yuanyuan Ping, Wangqing Kong
Summary: A nickel-catalyzed three-component defluorinative reductive cross-coupling reaction for the synthesis of functionalized gem-difluoroalkenes is reported.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kuai Wang, Jiachang Chen, Wenfeng Liu, Wangqing Kong
Summary: The introduction of fluorine-containing groups into organic molecules can significantly affect their physical and chemical properties and has been widely used in drug discovery and development. In this study, a nickel-catalyzed asymmetric cyclization reaction was described, which enables the efficient synthesis of synthetically attractive 4-fluorovinyl-substituted 2-pyrrolidones. This protocol shows high chemo-, regio-, and enantioselectivities and can be utilized in the synthesis of the antiepileptic drug Seletracetam.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Zhengtian Ding, Wangqing Kong
Summary: Carbonyl-containing oxindoles are ubiquitous core structures in many biologically active natural products and pharmaceutical molecules. Nickel-catalyzed reductive aryl-acylation and reductive aryl-esterification reactions provide 3,3-disubstituted oxindoles with ketone and ester functionality at the 3-position, respectively.
Review
Chemistry, Multidisciplinary
Qi Pan, Yuanyuan Ping, Wangqing Kong
Summary: The use of nickel catalysts in reductive cyclization/cross-coupling reactions allows the construction of valuable chiral heterocycles with quaternary stereocenters. This method offers advantages in building C(sp3)-C bonds, but limitations including low chemoselectivity and availability of organometallic nucleophiles restrict its application. This Account presents recent research on tuning the selectivity and cyclization mode of reductive cyclization/cross-couplings using nickel catalysts. It demonstrates the synthetic potential of this approach and the control of migratory aptitude through ligand modification and nickel oxidation state.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Sheng Xu, Yuanyuan Ping, Wei Li, Haoyun Guo, Yinyan Su, Ziyang Li, Minyan Wang, Wangqing Kong
Summary: In this study, we achieved enantioselective C(sp3)-H functionalization of undirected oxacycles using photo-HAT/nickel dual catalysis, allowing for the direct construction of high-value and enantiomerically enriched oxacycles from simple and abundant hydrocarbon feedstocks. The synthetic utility of this strategy was further demonstrated through late stage functionalization of natural products and the synthesis of pharmaceutically relevant molecules. Experimental and density functional theory calculation studies provided detailed insights into the mechanism and origin of enantioselectivity for the asymmetric C(sp3)-H functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Wenfeng Liu, Yang Ke, Chuhan Liu, Wangqing Kong
Summary: Here, we describe a method for the direct and selective acylation and alkynylation of C(sp(3))-H bonds of saturated hydrocarbons using synergistic decatungstate photo-HAT and nickel catalysis. This method exhibits excellent site selectivity and efficiently constructs a wide variety of high-value compounds from abundant hydrocarbon feedstocks.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Herong Chen, Zhijun Zhou, Wangqing Kong
Summary: The new nickel-catalyzed direct coupling reaction can directly convert alkenes and methanol into valuable allylic alcohols with good yield and selectivity, and has a wide range of applicable substrates. This method has also been successfully applied to the synthesis of [5,6]-bicyclic hemiacetals.
