Article
Chemistry, Organic
Shivani Choudhary, Nayan Gayyur, Nayan Ghosh
Summary: A novel ynamide scaffold was designed, synthesized, and applied to a gold-catalyzed and para-toluenesulfonic acid (PTSA)-assisted cascade cycloisomerization reaction for the synthesis of beta-pyrrole substituted alpha,beta-unsaturated ketones. The reaction exhibited stereoselectivity, with the E-isomer as the major product in low to moderate yield.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Romeric Galea, Gaelle Blond
Summary: In this study, [7,5]-fused bicyclic acetals, also known as furooxepines, were synthesized through a gold(I)-catalyzed domino reaction. This one-step reaction allows the formation of multiple bonds, heterocycles, and a tetrasubstituted carbon stereocenter with 100% atom economy.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Hu Tian, Hong-Ming Zhang, Liang Yin
Summary: In this article, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and alpha-substituted alpha,beta-unsaturated thioamides is described, which produces a series of chiral selenides with high to excellent enantioselectivity. The reaction shows a broad substrate scope for both selenols and alpha-substituted alpha,beta-unsaturated thioamides. The catalytic system is also successfully used for asymmetric selenation of beta-substituted alpha,beta-unsaturated thioamides. A [Cu-(R,R-P)-TANIAPHOS]-SePh species is identified by Se-77 NMR spectra, with a chemical shift at delta 462 ppm. Furthermore, a {[Cu-(R)-TOL-BINAP]-SePh}(2) species is characterized by X-ray analysis, confirming the formation of Cu-Se bond in the reaction. Finally, the straightforward transformations of the thioamide group to amine and thioester are demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Guo-Qing Jiang, Bin-Hong Han, Xian-Peng Cai, Jian-Ping Qu, Yan-Biao Kang
Summary: An iron-catalyzed direct aerobic alpha,beta-dehydrogenation of carbonyls has been reported using tert-butyl nitrite and N-hydroxyphthalimide as the co-catalyst system. This method allows for the production of a wide range of lactams, flavanones, lactone, and thiochromen-4-one in high yields without the need for extra transition metal reagents.
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, Organic
Rakesh K. Saunthwal, Kapil Mohan Saini, Nicolas Grimblat, Abhinandan K. Danodia, Sushil Kumar, Vincent Gandon, Akhilesh K. Verma
Summary: We describe an unconventional approach for the synthesis of highly decorated polyaromatic biaryls with excellent regioselectivity through site-selective Ag-catalyzed twofold electrophilic cycloisomerization followed by Au-catalyzed double C-H activation. DFT computations reveal that this reaction represents a rare example of C1-C5 endo-exo and C1-C6 endo-endo cycloaromatization, with the formation of the 6-membered ring predicted to be the result of an uncommon SEAr on a vinyl carbocation.
Article
Chemistry, Organic
Zi-Qi Hu, Xiang Li, Li-Xia Liu, Chang-Bin Yu, Yong-Gui Zhou
Summary: A concise and effective ruthenium-catalyzed asymmetric transfer hydrogenation was developed for the synthesis of cis-beta-substituted alpha-hydroxybutyrolactone derivatives with excellent yields and selectivities. This one-step reaction can construct two consecutive stereogenic centers and be scaled up without loss of activity. Additionally, the reductive products can be easily converted into useful building blocks.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhi-Zhou Pan, Deng Pan, Jia-Heng Li, Xiao-Song Xu, Liang Yin
Summary: Chiral azaarene compounds are synthesized through a copper(I)-catalyzed asymmetric conjugate addition reaction with (E)-beta-substituted alkenyl azaarenes as the substrate. The reaction shows good yields, Z/E ratios, and enantioselectivity. Various azaarenes can be used as substrates, and specific product outcomes depend on the configuration of the starting unsaturated azaarenes. DFT calculations provide insights into the selectivity-determining step and the origin of selectivities. The synthesized compounds have synthetic utility in various transformations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Anil Kumar Khatana, Vikram Singh, Manoj Kumar Gupta, Bhoopendra Tiwari
Summary: A novel method for the synthesis of 3,6-disubstituted alpha-pyrones via Michael addition/lactonization/elimination cascade reactions is reported in this study, showing promising research and application prospects.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Shashank Shandilya, Manash Protim Gogoi, Shubham Dutta, Akhila K. Sahoo
Summary: Ynamide, a unique species with inherited polarization of nitrogen lone pair electron to triple bond, has been widely used for the development of novel synthetic methods and the construction of unusual N-bearing heterocycles. This review provides an overall scenic view into the gold catalyzed transformation of ynamides, including their reactivity towards various transfer reagents and carbon nucleophiles.
Article
Chemistry, Organic
Xiu-Qin Dong, Xuanliang Yang, Gang Liu, Xun Xiang, Dezheng Xie, Jinyu Han, Zhengyu Han
Summary: Efficient Ni/(S,S)-Ph-BPE-catalyzed asymmetric hydrogenation of alpha-substituted alpha,beta-unsaturated phosphine oxides/phosphonates/phosphoric acids has been successfully developed, and a wide range of chiral alpha-substituted phosphine hydrogenation products were obtained in generally high yields with excellent enantioselective control (92%-99% yields, 84%->99% ee). This method features a cheap transition metal nickel catalytic system, high functional group tolerance, wide substrate scope generality, and excellent enantioselectivity. A plausible catalytic cycle was proposed for this asymmetric hydrogenation according to the results of deuterium-labeling experiments.
Article
Chemistry, Organic
Pathan Mosim Amin, Qi Cui, Shaozhong Wang, Zhi-Xiang Yu
Summary: A bimetallic protocol has been developed for the synthesis of (Z)-gamma-alkylidenebutenolide compounds from propargyl alpha-ketoesters. This method involves a gold-catalyzed acyloxy migration and a carbonyl-ene cyclization process, with DFT calculations suggesting a dual role for copper salt in facilitating the generation of active gold catalyst and promoting intramolecular carbonyl-ene reaction.
Article
Chemistry, Organic
Chen-Long Li, Yusheng Yang, Yi Zhou, Zhi-Xiang Yu
Summary: A formal [3+3+1] reaction was developed through gold(I)-catalyzed enyne cycloisomerization and rhodium(I)-catalyzed [6+1] reaction to synthesize aza-6/7 bicyclic compounds, hexahydrocyclohepta[c]pyridinones. DFT calculations revealed four steps involved in the [6+1] cycloaddition reaction of vinylspiropentanes and CO.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shitao Sun, Jinle Hao, Maosheng Cheng, Yongxiang Liu, Bin Lin
Summary: Computational studies provide insight into the regioselectivity of gold(i)-catalyzed intramolecular cycloisomerizations of tryptamine-ynamides. The electrostatic effect is found to be the key factor for alpha-position selectivity, while the dispersion effect is the key factor for beta-position selectivity. These findings guide the understanding of other gold(i)-catalyzed asymmetric alkyne cyclization reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Ajay Sharma, Satyendra Kumar Pandey
Summary: A novel and metal-free tandem approach for synthesizing alpha-substituted (E)-alpha,beta-unsaturated aldehyde derivatives has been developed, which involves acid-catalyzed epoxide rearrangement and organocatalyzed aldol condensation processes. This method exhibits a broad substrate scope and mild reaction conditions, resulting in moderate to high yields. Examples of large-scale reactions and the synthesis of bioactive molecules demonstrate the potential applicability of this method.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Ruben Pomar Fuentespina, Jose Angel Garcia de la Cruz, Gabriel Durin, Victor Mamane, Jean-Marc Weibel, Patrick Pale
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Fatih Sirindil, 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.
