Article
Chemistry, Organic
Christian B. J. Breuers, Constantin G. Daniliuc, Armido Studer
Summary: The stereoselective intramolecular dearomatizing spirocyclization of indoles via oxidative N-heterocyclic carbene (NHC) catalysis to afford indolenines bearing an all-carbon quaternary center at the 3-position is described. The reaction proceeds through the intramolecular nucleophilic addition of the indole to an in situ generated α,β-unsaturated acyl azolium.
Review
Chemistry, Multidisciplinary
Guangcai Xu, Gerrit J. Poelarends
Summary: The application of biocatalysis in challenging synthesis has greatly benefited from the development of new enzymes. By incorporating catalysis modes from synthetic chemistry, novel biocatalysts have been created, and the design of iminium catalysis plays a fundamental role in this process. It has been shown that repurposing existing enzymes or constructing artificial enzymes can promote valuable abiological transformations, demonstrating the power of combining chemomimetic biocatalyst design and directed evolution in generating new-to-nature enzymes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo, Yan-Cheng Hu, Boshun Wan, Qing-An Chen
Summary: Transition metal catalyzed decarbonylation offers a unique synthetic strategy for new chemical bond formation. The study developed a visible light induced rhodium catalysis for decarbonylative coupling of imides with alkynes under ambient conditions, revealing the rhodium complex serves as both the catalytic center and photosensitizer. This visible light promoted catalytic decarbonylation strategy opens up new opportunities for re-evaluating old transformations with ligand dissociation as a rate-determining step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fang Wang, Qianting Zhou, Xinying Zhang, Xuesen Fan
Summary: A novel and efficient alpha-C(sp(3))-H alkenylation of cyclic amines with maleimides was presented, featuring readily available and structurally diverse substrates, a green and economical catalyst, a unique reaction pathway, mild reaction conditions, high efficiency, and excellent atom economy. This new reaction enriches the application of Fe(III)-catalyzed C(sp(3))-H activation and functionalization.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Cong Zhang, Yuhang He, Guanghui An
Summary: Iron-mediated divergent reductive coupling reactions of heteroarenes with alkenes have been developed. By switching the substituent site at the C2 and C4 positions of quinolines, either C2 Minisci alkylation or C4 reductive alkylation could be achieved. These approaches feature mild conditions and sensitive functional group tolerance, which enables the functionalization of natural products and medicines. Mechanism investigation revealed that Fe(dibm)(3) would be a dual promoter for both alkyl radical transfer and generation of the more reactive hydrogen donor Ph(RO)SiH2.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Anna M. Costa, Alejandro Castro-Alvarez, Daniel Fillot, Jaume Vilarrasa
Summary: The energies of the CH2=CH-CH=N+R2 + HNR*(2) + CH2=CH-CH=N+R*(2) + HNR2 reactions and similar equilibria with cinnamaldehyde have been calculated and compared. The predicted order of stability of the iminium ions in very polar solvents differed from that in the gas phase. These findings can help predict the dominant iminium salts formed when conjugated carbonyl compounds are reacted with secondary amines and appropriate acids.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ji-Hang Xu, Zi-Kui Liu, Yan-Liu Tang, Yang Gao, Xiao-Qiang Hu
Summary: An unprecedented ring-opening cross-coupling of 1,2-oxazetidines with arylboronic acids using copper catalysis has been achieved. This reaction offers simple operation, inexpensive catalyst, broad scope, and high regioselectivity, leading to a wide range of aminomethylation products. Furthermore, the obtained products can be further transformed and bioactive acids can be modified.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Bijan Mirabi, Austin D. Marchese, Mark Lautens
Summary: In this study, a nickel-catalyzed cross-electrophile coupling reaction of aryl chlorides and heteroaryl chlorides was reported, enabled by a synergistic combination of halide effects and the addition of a magnesium salt. Electronic-deficient aryl chlorides were found to perform the best in the reaction, and preliminary mechanistic evidence showed that MgCl2 is crucial for accelerating the reduction of Ni(II) while small quantities of iodide lead to improved yields.
Article
Chemistry, Applied
Qi-Ying Zhang, Lu-Xin Li, Song-Lin Wang, Jing Ma, Hai-Ming Guo
Summary: An electrochemically-driven organocatalytic enantioselective oxidative coupling of tetrahydroisoquinolines and acrylaldehyde was developed, leading to various chiral C1-alkenyl tetrahydroisoquinolines derivatives with yields of 69-86% and er of 93:7-96:4. This synthetic route offers access to various optically active C1-substituted tetrahydroisoquinolines derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Valentina Pelliccioli, Davide Dova, Clara Baldoli, Claudia Graiff, Emanuela Licandro, Silvia Cauteruccio
Summary: Efficient and versatile synthetic routes to functionalized tetrathia[7]helicenes (7-THs) have been described in this study. Key intermediates were synthesized using palladium-catalyzed homocoupling reactions and annulation reactions. The versatility of bromides 1 for preparing a variety of 7-TH derivatives, including 7,8-disubstituted and 7-monosubstituted compounds, has been demonstrated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xinjie Li, Peng Qi, Hongguang Du
Summary: A metal-free cross-dehydrogenation coupling method was developed for the synthesis of N-9 alkylated purine derivatives. Thioethers were used as versatile alkylation reagents with PhI(OAc)2 as the oxidant, resulting in moderate to good yields. The regioselectivity of this method involving unsymmetrical thioethers and purine derivatives was also investigated.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Thomas Schneider, Maximilian Fleischmann, Daniel Hergesell, Nicola Majstorovic, Gerhard Maas
Summary: A convenient method for the synthesis of 4-trifluoromethyl-quinolines from 1-trifluoromethyl-prop-2-yne 1-iminium triflates and anilines has been reported. Various 4-CF3-quinolines with additional substituents and functional groups in different positions were prepared with high yields. Additionally, derivatives like N-substituted 4-CF3-quinolinium salts and pyrrolo[1,2-a:3,4-c']diquinoline bearing two CF3 substituents were successfully synthesized.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Yulia Volkova, Sergey Baranin, Igor Zavarzin
Summary: This review provides a general overview of the utility of A(3) coupling in the synthesis of heterocycles, highlighting the variety of compounds that can be directly accessed from single reactions. The diverse methodologies for the synthesis of N,O,S-heterocycles based on A(3) coupling are presented, emphasizing the influence of reaction conditions and the use of additional reagents on the outcome of the transformations.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Carter S. Gerke, Matthew Klenk, Peter Zapol, V. Sara Thoi
Summary: This study investigates the production of urea from environmentally harmful chemical feedstocks (CO2 and NO3-) through the optimization of electrolytes and pulsed potential electrolysis. It achieves a Faradaic efficiency of 60.4% and provides insights into the formation of C-N-related species and the impact of pulsed potential on substrate transport.
Article
Chemistry, Organic
Masashi Yokoya, Takaaki Ishiguro, Yoshiaki Sakairi, Shinya Kimura, Yuji Morita, Masamichi Yamanaka
Summary: A novel and efficient method for synthesizing benzo[de]chromene-7,8-dione derivatives without post-oxidation of benzo[de]chromenes was developed. The synthesized compounds exhibited strong antimicrobial activity, particularly against multidrug efflux pump-deficient strains.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
