Article
Chemistry, Organic
Yong Xu, Jiangtao Sun
Summary: This study describes the use of gold-catalyzed cascade cyclization and 1,3-difunctionalization of 2-(1-alkyny)-2-alken-1-ones with N,O-acetals, leading to the discovery of novel 1,3-oxyaminomethylation and 1,3-aminomethylamination. By varying reaction conditions, particularly the gold catalysts, these two distinct reaction pathways can be selectively controlled. Tandem cyclization and 1,4-oxyaminomethylation have also been achieved.
Article
Chemistry, Organic
Wen-Kang Wang, Hong-Ru Tan, Ning-Ning Wang, Hong-Li Ruan, Sheng-Yin Zhao
Summary: An efficient annulation method for the synthesis of polysubstituted dihydrofurans from 1,3-dicarbonyl compounds and maleimides is described. The reactions can afford furo[2,3-c]pyrrole derivatives with satisfactory yields. The developed strategy realizes the direct oxidative double C(sp(3))-H functionalization in the presence of copper(I) salts and 2-(terr-butylperoxy)-2-methylpropane. Meanwhile, this protocol features a mild reaction condition and simple catalytic system.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Bao Yu, Mohamed Selkti, Janick Ardisson, Marie-Isabelle Lannou, Geoffroy Sorin
Summary: A novel and straightforward approach to obtain cyclic conjugated enynes from readily available substrates with good yields has been developed using silver carbonate/DBU as catalyst. The reaction is easy to set up, broad in scope, and can be conducted in a one-pot fashion from easily accessible substrates through a series of reactions.
Article
Chemistry, Physical
Yang Gao, Simin Yang, Yanping Huo, Qian Chen, Xianwei Li, Xiao-Qiang Hu
Summary: A highly efficient NiH catalytic system was developed for the selective hydroamination of alkynes, leading to structurally diverse quinolines. This method is applicable to a wide range of alkynes and has shown utility in the functionalization of natural products and the synthesis of complex molecules. Preliminary mechanistic experiments suggest an alkenylnickel-mediated alkyne hydroamination and intramolecular cyclization of enamine intermediates.
Article
Chemistry, Organic
Anandarao Munakala, Rambabu Chegondi
Summary: A highly regioselective silver(I)-catalyzed intramolecular annulation method was reported in this study, which enables the synthesis of meta-substituted phenols with enone functionality from alkyne-tethered cyclohexadienones. The reaction proceeds through intramolecular 1,6-enyne cyclization, aromatization, and oxetene ring rearrangement, and is compatible with a wide range of C-tethered cyclohexadienones to afford indanes in high yields. The unique functionality of the products allows for further transformations to expand diversity.
Article
Chemistry, Multidisciplinary
Zhe Meng, Jun Yan, Chao Ning, Min Shi, Yin Wei
Summary: This paper presents an efficient synthetic strategy for the rapid construction of multisubstituted pyrroles, furans, and thiophenes via NXS mediated desulfonylative/dehydrogenative cyclization of vinylidenecyclopropanes. The method offers advantages such as a wide substrate range, high efficiency, and synthetic usefulness of the heterocyclic products under metal-free and mild conditions. The derivatization of pyrrole products and the preparation of functional molecules demonstrate the synthetic potential of the products as platform molecules. The reaction mechanism has been investigated through control experiments and DFT calculations.
Article
Chemistry, Organic
Xiao-Fang Song, Li-Jing Zhang, Xing-Guo Zhang, Hai-Yong Tu
Summary: A general and efficient method for synthesizing trifluoromethylated α-acyloxyketones has been developed through silver-catalyzed hydroacyloxylation of trifluoromethyl propynols with various acids. The obtained α-acyloxyketones can be easily hydrolyzed under acidic conditions to produce the corresponding trifluoromethylated α-hydroxyketones and undergo various further transformations.
Article
Chemistry, Multidisciplinary
Luo Ge, Syuzanna R. Harutyunyan
Summary: Chiral bisphosphine ligands play a key role in transition-metal-catalyzed asymmetric synthesis. However, the commonly used transition metals are expensive and scarce, and the synthesis of chiral phosphine ligands is complex. In this study, a catalytic asymmetric hydrophosphination reaction using a chiral complex of earth-abundant manganese(i) was developed. This reaction provides a short and efficient synthetic route to access easily obtainable and structurally tunable chiral bisphosphines, which can be used in asymmetric catalysis with earth-abundant metal-based organometallic catalysts.
Article
Chemistry, Organic
Haiyun Peng, Yangyi Zhang, Guisheng Deng
Summary: The silver(I)-catalyzed tandem reaction of enynones with 4-alkenylisoxazoles provides a convenient method for the synthesis of 2-(furan-2-yl)-1,2-dihydropyridines. The reaction proceeds through the formation of (2-furyl)metal carbene intermediate, N-O bond cleavage of 4-alkenyl isoxazoles/rearrangement, subsequent 6 pi electrocyclic reaction, and [1,5] H-shift. This atom-economic strategy allows for the efficient construction of both the 1,2-dihydropyridine skeleton and furan framework in a one-pot reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhi-Wei Wang, Yu Zheng, Yu-En Qian, Jian-Ping Guan, Wei-Dong Lu, Chu-Ping Yuan, Jun-An Xiao, Kai Chen, Hao-Yue Xiang, Hua Yang
Summary: This study reports on a new photoredox-catalyzed reaction that can synthesize a range of 3-aminochromones under mild conditions, and further expand the applications of this reaction by constructing diverse amino pyrimidines through downstream transformations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Shuitao Zhang, Jianxin Li, Tiebo Xiao, Baomin Yang, Yubo Jiang
Summary: An operationally simple method was developed for the synthesis of isoquinoline and quinazoline fused 1,2,3-triazoles, which can be applied to a variety of substrates containing functional groups to deliver novel compounds with good yields.
Article
Chemistry, Organic
Ping Wu, Liandi Wang, Kaikai Wu, Zhengkun Yu
Summary: This study addresses the challenge of the direct synthesis of triazole 2-oxides in the field of N-heterocyclic chemistry. By utilizing a novel copper-catalyzed nitrosylation/annulation cascade of enaminones and using noncorrosive tert-butyl nitrite, the synthesis of 1H-1,2,3-triazole 2-oxides with wide substrate scopes and good tolerance to various functional groups is achieved.
Article
Chemistry, Organic
Jorge Victoria-Miguel, William H. Garcia-Santos, Alejandro Cordero-Vargas
Summary: An efficient visible light catalyzed method for the preparation of 2,3-dihydrofurans using 2-bromoketoesters as radical precursors and alkyl enol ethers as acceptors was reported. The photoredox cycle provides an oxonium ion that is captured by an internal nucleophile to yield the corresponding dihydrofurans. The obtained products contain a versatile acetal moiety at C-2, allowing for the transformation into various heteroaromatic and nonaromatic compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Balati Hasimujiang, Shengsheng Lin, Chengwei Zheng, Yong Zeng, Zhixiong Ruan
Summary: A mild, practical method for the synthesis of various C-3 selenylated benzo[b]furan derivatives was developed via electrooxidation-promoted intramolecular cyclization of alkynes. The method exhibited high selectivity, high yield, and could easily be scaled up, providing rapid access to a diverse range of selenylated benzo[b]furans.
Article
Chemistry, Organic
Xuelin Yue, Yijie Gao, Junwei Huang, Yadong Feng, Xiuling Cui
Summary: An efficient method for synthesizing N substituted indenoisoquinolinones has been developed through rhodium(III)-catalyzed C-H bond activation/subsequent [4 + 2] cyclization. The reaction starts from readily available 2-phenyloxazolines and 2-diazo-1,3-indandiones. This protocol offers excellent atom- and step-economy, providing a novel strategy for the synthesis of N-substituted indenoisoquinolinones and enabling the study of their biological activities.
Article
Chemistry, Organic
Fatih Sirindil, Jean-Marc Weibel, Patrick Pale, Aurelien Blanc
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.