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, Organic
Jing Guo, Zi-Sheng Chen, Wen-Shuai Chen, Xin Zhao, Kegong Ji
Summary: A novel P,N-bidentate ligand-assisted gold-catalyzed oxidative amination of beta-amino-ynones has been developed, allowing the simple and efficient construction of various quaternary ammonium-olate salts in good to excellent yields. These unprecedented quaternary ammonium-olate salts can be isolated and purified via simple suction filtration. The broad substrate scope, easy purification, easy further transformation, and mild conditions make it a viable alternative for the synthesis of various quaternary ammonium-olate salts.
Article
Chemistry, Applied
Taku Shoji, Yukino Ariga, Naoko Sakata, Daichi Ando, Shigeki Mori, Tetsuo Okujima, Ryuta Sekiguchi, Shunji Ito
Summary: Bronsted acid-mediated intramolecular cyclization of 2-amidoazulene derivatives led to the formation of 2-perfluoroalkylazuleno[2,1-d]pyrimidin-4(3H)-ones. Heating of these products in phosphoryl chloride resulted in 4-chloro-2-perfluoroalkylazuleno[2,1-d]pyrimidines. The reactivity of these pyrimidin-4(3H)-ones and pyrimidine derivatives towards electrophilic and nucleophilic substitution reactions was evaluated, and various functional groups were found to be incorporated into these derivatives. NMR studies, NICS calculations, and single-crystal X-ray structure analyses revealed the structural features including bond-length alternation of the azuleno[2,1-d]pyrimidin-4(3H)-ones and pyrimidine derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Biochemistry & Molecular Biology
Taku Shoji, Mutsumi Takeuchi, Mayumi Uda, Yukino Ariga, Akari Yamazaki, Ryuta Sekiguchi, Shunji Ito
Summary: In this paper, a procedure for the synthesis of azuleno[2,1-b]quinolones and quinolines from 2-arylaminoazulene derivatives is described. The synthesis of azuleno[2,1-b]quinolones was achieved by the Bronsted acid-catalyzed intramolecular cyclization of 2-arylaminoazulene derivatives. The halogenative aromatization of azuleno[2,1-b]quinolones yielded azuleno[2,1-b]quinolines with a chlorine substituent at the pyridine moiety. The aromatic nucleophilic substitution reaction of these quinolines with secondary amines produced the corresponding aminoquinoline derivatives.
Article
Chemistry, Applied
Jun-Sheng Wei, Zi-Yu Xu, Yin Wei, Min Shi
Summary: In this paper, a gold(I)-catalyzed cascade cyclization of N- or O-nucleophile tethered-vinylidenecyclopropanes (VDCPs) is reported, leading to the synthesis of pyrrole, furan, pyrrolidine, and piperidine skeletons in 30%-98% yields. The reaction pathways depend on the carbon chain length connecting the nucleophile and VDCPs, resulting in different products. By using α-amino VDCPs and α-hydroxyl VDCPs with a methylene group as the connection, intramolecular nucleophilic addition and aromatization occur, followed by ring-opening of the cyclopropane unit to produce substituted pyrroles and furans. Extending the chain length to three or four carbons enables the formation of pyrrolidines and piperidines with a cyclobutene moiety through ring expansion of the cyclopropane unit and gold carbene induced vinylogous nucleophilic addition.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Jian Li, Haibo Huo, Fang Yang, Qianqian Zhou, Mengxue Li, Zi-Sheng Chen, Kegong Ji
Summary: A gold(III)-catalyzed cascade oxidation/cyclization reaction using different N-oxides with distinct nucleophilic properties has been reported for the assembly of diverse polycycles. The synthesized compounds show promising antibacterial activity and could be utilized for the synthesis of bioactive molecules.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Yiming You, Jiayue Wu, Lixin Yang, Tao Wu
Summary: In this work, a nickel-catalyzed reductive defluorination of iodo allyl gem-difluorides to allenyl monofluorides was developed under mild conditions, showing good functional group tolerance. The obtained monofluoroallenes can be easily converted to other C-F bond compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Mingshi Pan, Xiabin Wang, Yixin Tong, Xiaodong Qiu, Xiaobao Zeng, Biao Xiong
Summary: A new strategy for the direct synthesis of functionalized pyrroles from beta-amino alcohols and ynones has been demonstrated. This method proceeds in an atom- and step-economic fashion and offers the advantages of broad substrate scope, operational simplicity, and water and hydrogen gas as the sole by-products, providing an alternative and sustainable path to access functionalized pyrroles.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Guanyu Zhou, Zhibin Huang, Xu Xu, Zhang Fang, Pengcheng Huang, Zefeng Deng, Bao Li, Yingsheng Zhao
Summary: A practical method using rhodium as the catalyst to synthesize quinoxalinones via intra/intermolecular amination has been developed, with a wide variety of products obtained in moderate to excellent yields. Gram-scale reactions were also achieved, highlighting the synthetic importance of this new transformation.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Tian-Ci Wang, Ling Zhu, Shiwei Luo, Zhong-Sheng Nong, Pu-Sheng Wang, Liu-Zhu Gong
Summary: Asymmetric functionalization of the C(sp(3))-H bond using chiral phosphoramidite-palladium catalysis was successfully achieved in this study, leading to the synthesis of enantioenriched beta-amino-gamma,delta-unsaturated carbonyl derivatives and providing a key intermediate for the asymmetric synthesis of Focalin. The research also revealed an umpolung reactivity of N-allylimines through a concerted proton and two-electron transfer process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Surajit Duari, Subrata Biswas, Arnab Roy, Srabani Maity, Abhishek Kumar Mishra, Aguinaldo R. Souza, Asma M. Elsharif, Nelson H. Morgon, Srijit Biswas
Summary: In this study, a catalytic synthetic strategy was developed to access various N-functionalized heterocyclic derivatives. The reaction involves the direct nucleophilic substitution of alcohols followed by X to N alkyl group migration. Methyl trifluoromethanesulfonate was found to be an efficient catalyst for this reaction. The mechanism was elucidated through experiments and DFT calculations.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Lin-Jun Qi, Chong-Yang Shi, Peng-Fei Chen, Long Li, Gang Fang, Peng-Cheng Qian, Chao Deng, Jin-Mei Zhou, Long-Wu Ye
Summary: The study presents a novel gold-catalyzed 1,1-carboalkoxylation method for the synthesis of valuable cyclic compounds, enabling asymmetric synthesis through a chirality-transfer strategy. Further mechanistic insight into the distinct migration into gold carbenes is supported by theoretical calculations.
Article
Chemistry, Organic
Lubomir Vana, Martin Jakubec, Jan Sykora, Ivana Cisarova, Jan Storch, Vladimir Cirkva
Summary: A novel methodology for the successful synthesis of aza[n]-phenacenes was developed, introducing nitrogen atoms to induce changes in physicochemical properties. The important characteristics of the prepared aza[n]phenacenes were studied experimentally and compared to their carbo analogues. Features of the crystalline aza[n]phenacenes were also investigated, including intermolecular interactions and changes in solubility or melting points.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Mauro Mato, Feng Wang, Josep Cornella
Summary: This study reveals how an N,C,N-bismuthinidene can promote an intramolecular conjugate amination, resulting in high yields of cyclic carbamates. The reaction occurs at room temperature and has short reaction times, requiring a low loading of a bismuth(I) complex without the need for an additional Bronsted base. Preliminary mechanistic studies suggest that the reaction proceeds through a polar pathway involving the conjugate addition of the nucleophilic bismuthinidene followed by an intramolecular aza-Michael reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mariya A. Panova, Konstantin V. Shcherbakov, Yanina V. Burgart, Victor I. Saloutin, I. Ya. Postovsky
Summary: The formation of various fluorine atoms substitution products in Cs2CO3-promoted SNAr reactions of 2-(poly-fluoroaryl)-4H-chromen-4-ones with pyrazole in refluxing MeCN was demonstrated. Selective synthesis of mono(1H-pyrazol-1-yl)- and per(1H-pyrazol-1-yl)flavones was achieved by using different pyrazole and base equivalents in the presence of NaOBut at room temperature. A mechanism involving the substitution of fluorine atoms in 2-(penta-fluorophenyl)-4H-chromen-4-one by sodium pyrazolide was proposed, and the structures of pyrazolyl-substituted flavones were determined based on NMR and XRD data.
JOURNAL OF FLUORINE CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
John H. Reed, Pavel A. Donets, Solene Miaskiewicz, Nicolai Cramer
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Organic
Romain Pertschi, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
Article
Chemistry, Organic
Fatih Sirindil, Stephane Golling, Raphael Lamare, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
Article
Chemistry, Inorganic & Nuclear
Romain Pertschi, Delphine Hatey, Patrick Pale, Pierre de Fremont, Aurelien Blanc
Review
Chemistry, Multidisciplinary
Remi Jouhannet, Samuel Dagorne, Aurelien Blanc, Pierre de Fremont
Summary: This article summarizes the synthesis and applications of well-defined gold(III) complexes reported over the last fifteen years, exploring the applications of gold catalysis in organic chemistry and the potential of gold(III) complexes in pharmacology.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Romain Pertschi, Adiran de Aguirre, Patrick Pale, Aurelien Blanc, Amalia I. Poblador Bahamonde
Summary: The Au(I)-catalyzed reactions of (2-alkynyl)phenylsulfonyl azetidines were studied via DFT calculations, revealing the preference for nucleophilic addition over direct ring opening. Experimental reverse regioselectivity was also explored, with two scenarios regarding the activation of alkynes by Au(I) species. Competitive pathways were identified, with mono Au(I) complexes leading to final products in agreement with experiments. Further discussion on the importance of excess protic nucleophile on protodemetallation step and final aminal formation was also provided.
HELVETICA CHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Fatih Sirindil, Romain Pertschi, Emma Naulin, Delphine Hatey, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
Summary: The Suzuki-Miyaura cross-coupling reactions of aryl/vinyl sulfonates/halides with various boron species were successfully carried out using an easily available trans-dichlorobis(XPhos)palladium(II) precatalyst under microwave assistance, resulting in more than 30 coupling products with yields up to 99%, including the synthesis of bioactive compounds. A mechanistic investigation of the reaction was conducted using nuclear magnetic resonance (NMR) and high-resolution mass spectroscopy, revealing the nature of the active Pd-0 species and the reducing entity.
Review
Biochemistry & Molecular Biology
J. Obszynski, H. Loidon, A. Blanc, J. -m. Weibel, P. Pale
Summary: This article discusses the importance of antibiotics and their impact on bacteria, particularly in terms of aging and resistance. It focuses on the chemical synthesis of aminoglycosides and the structure-activity relationships in order to identify efficient modifications that can convert them into future drugs. These studies are of great significance for the development of clinically viable drug candidates.
BIOORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Solene Miaskiewicz, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
Summary: This article presents an efficient method for synthesizing the 2,3-dihydropyrrolo[1,2-a]indole motif using gold catalysis on N-aryl 2-alkynylazetidine derivatives. Attempts to apply this method to the synthesis of harmalidine resulted in the discovery of a surprising 12-membered diimino dimer, but the reported structure of harmalidine could not be reached from the intermediates obtained.
Review
Biochemistry & Molecular Biology
Fatih Sirindil, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
Summary: This review describes the known total and formal syntheses of the members of the rhazinilam family, which have unique structures and taxol-like antimitotic activities.
NATURAL PRODUCT REPORTS
(2022)
Article
Chemistry, Physical
Romain Pertschi, Solene Miaskiewicz, Nicolas Kern, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
Summary: Gold(I) catalysts enable the chemoselective addition of tailor-made N-sulfonylated azetidine derivatives onto alkynes, leading to the formation of bicyclic vinyl-ammonium gold intermediates. These intermediates can efficiently produce ring-expanded azepine products, which are important pharmacophore fragments. Divergent deauration pathways occur depending on the substitution pattern of the starting material, yielding monomeric or original dimeric nitrogenated seven-membered rings in good to excellent yields with high stereoselectivity. Overall, the study demonstrates the synthetic potential of ammoniumation catalyzed by gold for the future development of reaction cascades and preparation of bioactive compounds.
