Article
Chemistry, Applied
Yan-Rui Zhao, Lei Li, Jun Xuan
Summary: In this study, a direct synthesis method for indolines through visible-light irradiation at room temperature without the addition of any photocatalysts and additives was reported. Mechanism studies showed the formation of an electron donor-acceptor complex between iodonium ylides and tertiary aryl amines during the reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Thomas Delouche, Elsa Caytan, Marie Cordier, Thierry Roisnel, Gregory Taupier, Yann Molard, Nicolas Vanthuyne, Boris Le Guennic, Muriel Hissler, Denis Jacquemin, Pierre-Antoine Bouit
Summary: We report a straightforward synthesis method for novel P-heterocycles. These compounds exhibit good stability and can be post-functionalized with different substituents. They are also suitable for the preparation of more complex polyaromatic scaffolds. Our study shows that molecular engineering can not only tune the optical properties of these compounds but also impart them with special optical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yulong Wang, Shenyu Shen, Chonglong He, Youkang Zhou, Keyuan Zhang, Bin Rao, Tian Han, Yaqiong Su, Xin-Hua Duan, Le Liu
Summary: Here, we report a practical copper-mediated direct intramolecular cyclopropanation of distal olefinic acetate to synthesize cyclopropane-fused gamma-lactones and lactams. This cascade reaction proceeds through a hydrogen atom transfer-induced radical cyclization and copper-mediated cyclopropanation sequence. The protocol features high atom- and step-economy, excellent diastereoselectivity, broad tolerance of functional groups, and operational simplicity.
Article
Chemistry, Multidisciplinary
Giedre Sirvinskaite, Celine S. Nardo, Patrick Mueller, Aurelio C. Gasser, Bill Morandi
Summary: In this study, a metal-free intramolecular benzylic sp(3) C-H amination using aryl nitro compounds as aryl nitrene precursors was disclosed. The organosilicon reagent N,N'-bis(trimethylsilyl)-4,4'-bipyridinylidene (Si-DHBP) served as an efficient reductant, enabling the in-situ generation of aryl nitrene species for the direct and metal-free synthesis of unprotected 2-arylindolines from the corresponding nitroarene compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Aleksa Milosavljevic, Connor Holt, Alison J. Frontier
Summary: Herein, a one-pot nitrogen-interrupted halo-Prins/halo-Nazarov coupling cascade is reported, which enables the synthesis of functionalized cyclopenta[b]indolines with up to four contiguous stereocenters by joining an enyne and a carbonyl partner. A general method for alkynyl halo-Prins reaction of ketones is provided for the first time, allowing the formation of quaternary stereocenters. The outcomes of secondary alcohol enyne couplings and the impact of aniline enyne substituents on the reaction are also described.
Article
Chemistry, Multidisciplinary
Janos T. Csenki, Balazs L. Toth, Ferenc Beke, Balint Varga, Peter P. Feher, Andras Stirling, Zsuzsanna Czegeny, Attila Benyei, Zoltan Novak
Summary: This study reports a novel dyotropic rearrangement process involving the migration of iodine atoms in alkyl fragments, demonstrated through experimental and DFT studies. A new fluoroalkyl iodonium reagent was designed and synthesized using the dyotropic rearrangement, showing excellent fluoroalkylation activity towards various amines and nitrogen heterocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jiayong Zhang, Zhengjie He
Summary: A Lewis base-catalyzed intramolecular vinylogous aldol reaction has been developed for the synthesis of 3-hydroxy-2,3-disubstituted dihydrobenzofurans and indolines with high yields, excellent chemoselectivity, and diastereoselectivity. The resulting products can be further utilized for the synthesis of 2-alkenyl benzofurans and indoles through acid-promoted dehydration.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jiwon Jang, Hanbyul Kim, Seunghoon Shin
Summary: This study reports a revised mechanism for the gold-catalyzed enantioselective thioallylation of propiolates, which delivers highly enantio-enriched alpha-allyl-beta-thioacrylates. The research reveals that the competitive binding of thioethers as nucleophiles to the catalytic site inhibits its activity. The revised mechanism suggests that the conjugate addition of thioethers is the slowest step, followed by a rapid rearrangement, indicating the efficacy of the sulfonium-based approach in accelerating Claisen rearrangement.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Viktor A. A. Il'in, Elena V. V. Pyzhik, Anton B. Balakhonov, Maksim A. A. Kiryushin, Evgeniya V. V. Shcherbatova, Andrey A. A. Kuznetsov, Pavel A. A. Kostin, Andrey V. V. Golovin, Vladimir A. A. Korshun, Vladimir A. A. Brylev, Kseniya A. A. Sapozhnikova, Alexey M. M. Kopylov, Galina V. V. Pavlova, Igor N. N. Pronin
Summary: Central nervous system tumors related to gliomas account for about 30% of all primary brain tumors. Surgical attack is the main treatment approach as there is no effective therapy for glioma. The use of PET imaging methods, such as positron emission tomography, can enhance the accuracy of glioma removal by distinguishing malignant tissue. However, PET lacks specific visualization of cells with certain molecular markers. In this study, aptamers were used to enhance specificity in imaging tumor cells bearing the epidermal growth factor receptor (EGFR). Conjugates of aptamers specific to EGFR were successfully obtained and can be used for further PET analysis on model animals with grafted glioblastoma.
Article
Multidisciplinary Sciences
Gang Wang, Ran Lu, Chuangchuang He, Lei Liu
Summary: The study discusses the challenges and methods of catalytic kinetic resolution of amines, specifically focusing on the titanium-catalyzed asymmetric oxygenation with hydrogen peroxide. This approach allows for the efficient production of enantiopure hydroxylamines from secondary amines, demonstrating high chemoselectivity and enantio-discrimination. Late-stage asymmetric oxygenation of bioactive molecules is also explored in this research.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Anton Nenashev, Dmitrii Dospekhov, Mikhail Zavaruev, Ilia Potapov, Irina Levina, Vitaly Roznyatovsky, Andrey Mironov, Sergey Pisarev, Anna Pavlova, Tatyana Podrugina
Summary: A series of phosphonium ylides and mixed phosphonium-iodonium ylides, representing a new structural type, have been synthesized. This study highlights the correlation between the stability of the ylides and the nature of the electron-withdrawing groups. We delve into the impact of the structural variations within the phosphonium fragment on the rotational barrier of the C-C bond in carbonyl ylides.
Article
Chemistry, Multidisciplinary
Clemence Maingueneau, Marion Berdal, Romain Eychenne, Joelle Gaschet, Michel Cherel, Jean-Francois Gestin, Francois Guerard
Summary: Despite the growing interest in radioiodine and At-211-labeled radiopharmaceuticals, the research on radiolabeling reactions has been neglected, resulting in limited available synthetic strategies. This study compared the nucleophilic I-125 and At-211 labeling of aryliodonium ylides, and found that At-211 labeling was efficient on various precursors. The activation state of the aryliodonium ylides and reaction conditions played important roles in achieving high radiochemical yields and molar activity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Yan-Rui Zhao, Lei Li, Guo-Yong Xu, Jun Xuan
Summary: A new method for the construction of all-carbon tetra-substituted olefins using visible-light promoted coupling of diazo compounds with iodonium ylides has been developed, resulting in a wide range of products in moderate to good yields. The synthetic value of this method was demonstrated through the synthesis of natural isolates modified alkenes and the successful transformation of final olefins into important heterocycles.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Irene Martin, Cristina Aragoncillo, Pedro Almendros
Summary: This research has achieved a selective palladium-catalyzed reaction sequence, leading to the synthesis of novel 2-iodo-1-aryl-9H-carbazoles. The observed formation of 2-iodocarbazoles in contrast to gold catalysis suggests a metal-controlled cyclization through chemo- and regioselective alkyl migration and iodonium migration.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Siqi Wang, Jian-Shu Wang, Zhengjie Le, Jun Ying, Xiao-Feng Wu
Summary: A palladium-catalyzed dicarbonylation reaction has been developed for the synthesis of aryl esters from p-benzoquinones and aryl triflates using Cr(CO)(6) as the CO source. The reaction proceeds smoothly and efficiently, yielding a series of aryl esters in moderate to good yields (up to 90%).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bo Li, Cheng-Wei Ju, Wenlong Wang, Yanwei Gu, Shuai Chen, Yongrui Luo, Haozhe Zhang, Juan Yang, Hai-wei Liang, Mischa Bonn, Klaus Mu''llen, William A. Goddard, Yazhou Zhou
Summary: The study reports a heterogeneous single-atom Pt-catalyzed Heck reaction, the first of its kind on SACs, using a supercritical carbon-dioxide-assisted protocol. The research showcases how SACs can introduce underexplored coordination structures, offering potential for transferring migratory-insertion-based reactions to heterogeneous SACs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Yongrui Luo, Yuli Li, Jian Wu, Xiao-Song Xue, John F. Hartwig, Qilong Shen
Summary: This study reports the mechanism of carbon-halogen bond cleavage in copper-catalyzed cross-coupling reactions. Stable copper(III) complexes were successfully synthesized through oxidative addition reactions, and different reaction pathways were explored. Additionally, it was found that ligand can accelerate the oxidative addition, which is consistent with observations in other copper-catalyzed coupling reactions.
